1
DESCRIPTION
METHOD OF PRODUCTION OF ETHYLENE-BASED POLYMER PARTICLES AND
STRETCH-MOLDED ARTICLE OBTAINED FROM THE ETHYLENE-BASED POLYMER
5 PARTICLES
TECHNICAL FIELD
[OOOl]
Thepresentinventionrelatestoaproductionmethodcapable
10 of obtaining ultrahigh molecular weight ethylene-based polymer
particles havingexcellentstretchmoldabilityandfurtherhaving
excellent handleability industrially. Moreover, the present
invention relatesto a stretch-moldedarticleproducedusing such
particlesandastretch-moldedarticlethatispreferablyproduced
15 by a solid-phase stretch-molding method.
BACKGROUND ART
[0002]
So-called ultrahigh molecular weight ethylene-based
20 polymers, which have extremely high molecular weight, are
excellent in impact resistance, abrasion resistance, chemical
resistance, strength and the like, as compared with
general-purpose ethylene-basedpolymers, and thus have excellent
characteristics as engineering plastics.
SF-2399
a
[0003]
On the other hand, it is saidthatultrahighmolecularweight
ethylene-based polymers are not suitable for melt molding, which
is ageneralresinmoldingmethod, because oftheir highmolecular
5 weight. For this reason, molding methods of ultrahigh molecular
weight ethylene-based polymers have been developed such as a
method in which an ultrahigh molecular weight ethylene-based
polymer is dissolved in a solvent and molded, a solid-phase
stretch-molding method in which the ultrahigh molecular weight
10 ethylene-based polymer particles are stretched after
compression-bondingatatemperatureequaltoorbelowthemelting
point of the polymer, and the like.
[0004]
Patent Document 1 discloses that strength of the molded
15 article molded by the solid-phase stretch-molding method using
ultrahigh molecular weight polyethylene obtained using a
post-metallocene catalyst described in Patent Document 2
( [3-t-Bu-2-0-C6H3CH=N( C6F5)]* TiC12) becomes greater than or equal
to 3 GPa. However, according to the polymerization method
20 described in Patent Document 1, there is no use of a carrier, such
as an inorganic solid component and the like, for support of the
aforementioned catalyst component. Thus, during the
polymerization reaction, it is anticipated that there will be the
occurrence of the phenomenon of attachment of the polymer to the
SF-2399
# 3
polymerization reactor walls, agitator blades, or the like, i. e.
so-called fouling. It is therefore assumed that stable
industrial production would be extremely difficult using the
ethylene-based polymer production method described in Patent
5 Document 1. Furthermore, a large amount of expensive
organoaluminumoxy compound is required as a co-catalyst in order
to exert high catalytic activity in this method. Thus a separate
deashing step becomes necessary in order to remove the inorganic
components contained in the polymer, and it is anticipated that
10 cost will become extremely high during industrial production.
[0005]
On the other hand, suppression of fouling in production of
an ultrahigh molecular weight ethylene-based polymer is possible
by use of a supported type catalyst such as a titanium-based
15 supported type catalyst using a magnesium compound as a support
as described in Patent Documents 3, 4, or the like, or, by use
of a supported type catalyst in which a transition metal compound
is supported on an inorganic solid component formed from Si02
treatedwith an organoaluminumoxy compoundas describedin Patent
20 Document 5, or the like. Industrial production is known to be
possible due to the ability to suppress fouling by the use of a
supported type catalyst. However, a molded article with
sufficient strength is not obtainedusingthe ultrahighmolecular
weight ethylene-basedpolyrner particles produced usingthis type
of supported type catalyst, even when the ultrahigh molecular
weight ethylene-based polymer particles are solid-phase
stretch-molded (Patent Document 6 or the like).
5 PATENT DOCUMENTS
[0006]
Patent Document 1: W02009/007045 Pamphlet
Patent Document 2: Japanese Hll-315109A
Patent Document 3: Japanese H3-130116A
10 Patent Document 4: Japanese H7-156173A
Patent Document 5: Japanese 2000-297114A
Patent Document 6: Japanese H9-254252A
DISCLOSURE OF THE INVENTION
Problems to be Solved by 15 the Invention
[0007]
From the standpoint of the aforementioned background
technology, the problem to be solved by the present invention is
to provide a production method capable of obtaining ultrahigh
20 molecular weight ethylene-based polymer particles having
excellent stretch moldability and handleability industrially,
and further capable of obtaining such particles inexpensively.
A further problem of the present invention is to provide a
stretch-molded article produced using such particles.
Means for Solving the Problem
[0008]
As a result of investigations to solve the aforementioned
5 problems, the present inventionwas accomplishedbytheinventors
by discovery of a method of production of ethylene-based polymer
particles in the presence of an olefin polymerization catalyst
includinga specific transitionmetal compoundand fine particles
obtained through a specific process. Furthermore, the Patent
10 Documents 1 to 6 contain no mention of an example combining the
transition metal compound and fine particles of the present
invention, neither disclose or suggest that the ethylene-based
polymer particles obtained using the olefin polymerization
catalyst obtained by this combination are preferred for physical
15 properties after stretch-molding.
[0009]
That is to say, the method of production of the
ethylene-based polymer particles of the present invention
includes the step of:
20 homopolymerizing ethylene or copolymerizing ethylene and
a linear or branched a-olefin having 3 to 20 carbon atoms in the
presence of an olefin polymerization catalyst comprising:
(A) fine particles having an average particle diameter
greater than or equal to 1 nm and less than or equal to 300 nm
I 6
obtained by at least the following steps:
(Step 1) causing contact between a metal halide and an
alcohol in a hydrocarbon solvent;
(Step 2) causing contact between a component obtained by
5 (Step 1) and an organoaluminum compound and/or an
organoaluminumoxy compound; and
(B) a transition metal compound represented in following
General Formula .(I) or (11) :
[OOlO]
[OOll]
(in Formula (I), M is a transition metal atom of Group 4 or 5 in
the periodic table;
m is an integer ranging from 1 to 4;
15 R1 to R5 are the same or different and are a hydrogen atom,
halogen atom, hydrocarbon group, heterocyclic compound residue,
oxygen-containing group, nitrogen-containing group,
boron-containing 9rOuP1 sulfur-containing grOuPf
phosphorous-containing group, silicon-containing group,
20 germanium-containing group, or tin-containing group, wherein a
ring is optionally formed by bonding together of at least 2 such
groups;
R~ is selected from the group consisting of a hydrogen atom,
hydrocarbon groups having 1to 4 carbon atoms and composed of only
primary or secondary carbon atoms, aliphatic hydrocarbon groups
5 having at least 5 carbon atoms, aryl group-substituted alkyl
groups, monocyclic or bicyclic alicyclic hydrocarbon groups,
aromatic hydrocarbon groups, and halogen atoms;
n is a number satisfying valance number of M;
X is a hydrogen atom, halogen atom, hydrocarbon group,
10 oxygen-containing group, sulfur-containing group,
nitrogen-containing group, boron-containing group,
aluminum-containing group, phosphorous-containing group,
halogen-containing group, heterocyclic compound residue,
silicon-containing group, germanium-containing group, or
15 tin-containing group; where multiple groups indicated by X may
be the same or different when n is greater than or equal to 2;
andoptionallymultiple groupsindicatedbyxforma ringbymutual
bonding)
[0013]
(in Formula (11), M is titanium, zirconium, or hafnium;
R" to R" may be the same or different and are a hydrogen
atom, halogen atom, hydrocarbon group, heterocyclic compound
5 residue, oxygen-containing group, nitrogen-containing group,
boron-containing GlrouP, sulfur-containing group,
phosphorous-containing group, silicon-containing group,
germanium-containing group, or tin-containing group, wherein two
or more adjacent groups maybe optionallybondedtogetherto form
10 a ring;
X' and x2 are the same or different and are a hydrocarbon
group, oxygen-containing group, sulfur-containing group,
silicon-containing group, hydrogen atom, or halogen atom; and
Y is a divalent hydrocarbon group, divalent halogenated
hydrocarbon group, divalent silicon-containing group, divalent
germanium-containing group, divalent tin-containing group, -0-,
-CO-, -S-, -SO-, -SO2-, -Ge-, -Sn-, -NR-, -P (R) -, -P (0) (R) -, -BR-,
or -AIR- [wherein R is the same or different and is a hydrogen
atom, halogen atom, hydrocarbon group, halogenated hydrocarbon
20 group, or alkoxy group] ) ; and
( E ) anintrinsicviscosity [I]] oftheethylene-basedpolymer
particles, measured in decalin at 135'~, is from 5 to 50 dL/g.
In the present invention, the alcohol used in Step 1 in
obtaining the (A) fine particles is preferably a combination of
two types of alcohols s e l e c t e d fromalcohols h a v i n g l t o 25 carbon
atoms, anddifference i n carbonnumber o f t h e two types of alcohols
is preferably g r e a t e r than or equal t o 4. Moreover, these
alcohols are preferably a combination of an alcohol having 2 t o
5 12 carbon atoms and an alcohol having 13 t o 25 carbon atoms, or
a l t e r n a t i v e l y , are a combination of two types of alcohols selected
from alcohols having 2 t o 12 carbon atoms.
[0014]
In the present invention, f o r the (B) t r a n s i t i o n metal
10 compound, MinGeneral Formula (I) p r e f e r a b l y i s a t r a n s i t i o n m e t a l
atom of Group 4 i n the periodic t a b l e ; m preferably is 2; R'
p r e f e r a b l y i s agroupselectedfromlinearorbranchedhydrocarbon
groups having 1 t o 20 carbon atoms, a l i c y c l i c hydrocarbon groups
having3to20 carbonatoms, andaromatichydrocarbongroupshaving
15 6 t o 20 carbon atoms; R2 t o R5 may be the same or d i f f e r e n t and
preferably are a hydrogen atom, halogen atom, or hydrocarbon
group; ~ ~ ~ r e f e r a bsell~ecitesd fromaliphatichydrocarbongroups
having a t l e a s t 5 carbon atoms, a r y l group-substituted alkyl
groups, monocyclic or b i c y c l i c a l i c y c l i c hydrocarbon groups, and
20 aromatic hydrocarbon groups; and X preferably is a hydrogen atom,
halogen atom, or hydrocarbon group.
[0015]
In the present invention, the homopolymerization of
ethylene, or the copolymerization of ethylene and a l i n e a r or
1 branched a-olefin having 3 to 20 carbon atoms, is preferably
performed in a multi-stage polymerization.
[0016]
The ethylene-based polymer particles of the present
5 invention are characterized by being obtained by the production
method, and an average particle diameter of the ethylene-based
polymer particles being within a range greater than or equal to
10 nm and less than 3,000 nm.
[0017]
10 The method for production of a stretch-molded article
according to the present invention is characterized by using
ethylene-based polymer particles obtained by the production
method.
[0018]
15 In the present invention, the stretch-molded article is
preferably obtained by a solid-phase stretch-molding method.
[0019]
The stretch-molded article of the present invention is
obtainedbythe productionmethod forthe stretch-molded article.
20
EFFECT OF THE INVENTION
[0020]
By including the fine particles obtained via a specific
process as an essential constituent component of the olefin
1 polymerization catalyst, the method of production of
ethylene-based polymer particles of the present invention can
suppress fouling of the polymerization reactor walls, agitator
blade, or the like by the ethylene-based polymer particles to the
5 minimum degree, and is further capable of obtaining a molded
article with high strength by stretch-molding the ethylene-based
polymer particles obtained by this method. In this manner, the
present invention balances to a high degree industrial advantage
in the production of the ethylene-based polymer particles and
10 superiority in physical properties ofthe ethylene-basedpolymer
particles.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021]
FIG. 1isanSEMphotographoftheethylenepolymerparticles
of Example 1.
FIG. 2 is a photograph of the inside of the polymerization
reactoraftercompletionofthepolymerizationreactionofExample
1.
FIG. 3isanSEMphotographoftheethylenepolymerparticles
of Example 2.
FIG. 4 is a photograph of the inside of the polymerization
reactoraftercompletionofthepolymerizationreactionofExample
2.
SF-2399 * 12
FIG. 5isanSEMphotographoftheethylenepolymerparticles
of Example 3.
FIG. 6 is a photograph of the i n s i d e of the polymerization
reactoraftercompletionofthepolymerizationreactionofExample
5 3.
FIG. 7 i s anSEMphotographoftheethylenepolymerparticles
of Example 4.
FIG. 8 is a photograph of the i n s i d e of the polymerization
reactoraftercompletionofthepolymerizationreactionofExample
10 4 .
FIG. 9 i s an SEMphotographofthe ethylenepolymerparticles
of Example 5.
FIG. 10 is a photograph of the i n s i d e of the polymerization
reactoraftercompletionofthepolymerizationreactionofExample
15 5.
FIG. 11 is an SEM photograph of the ethylene polymer
p a r t i c l e s of Example 6.
FIG. 12 i s a photograph of the i n s i d e of the polymerization
reactoraftercompletionofthepolymerizationreactionofExample
20 6.
FIG. 13 is an SEM photograph of the ethylene polymer
p a r t i c l e s of Example 7.
FIG. 14 is a photograph of the i n s i d e of the polymerization
reactoraftercompletionofthepolymerizationreactionof~xample
F I G . 15 is an SEM photograph of the ethylene polymer
particles of Example 8.
F I G . 16 is a photograph of the inside of the polymerization
5 reactoraftercompletionofthepolymerizationreactionofExample
8.
F I G . 17 is an SEM photograph of the ethylene polymer
particles of Example 9.
F I G . 18 is an SEM photograph of the ethylene polymer
10 particles of Example 10.
F I G . 19 is a photograph of the inside of the polymerization
reactoraftercompletionofthepolymerizationreactionofExample
10.
F I G . 20 is an SEM photograph of the ethylene polymer
15 particles of Example 11.
F I G . 21 is a photograph of the inside of the polymerization
reactoraftercompletionofthepolymerizationreactionofExample
11.
F I G . 22 is an SEM photograph of the ethylene polymer
20 particles of Example 12.
F I G . 23 is a photograph of the inside of the polymerization
F I G . 24 is an SEM photograph of the ethylene polymer
9
particles of Example 13.
F I G . 25 is a photograph of the inside of the polymerization
reactor after completionofthe polymerization reactionof Example
13.
5 F I G . 26 is an SEM photograph of the ethylene polymer
particles of Example 14.
F I G . 27 is a photograph of the inside of the polymerization
reactoraftercompletionofthepolymerizationreactionofExample
14.
10 F I G . 28 is an SEM photograph of the ethylene polymer of
Comparative Example 1.
F I G . 29 is a photograph of the inside of the polymerization
reactor after completion of the polymerization reaction of
Comparative Example 1.
15 F I G . 30 is an SEM photograph of the ethylene polymer of
Comparative Example 2.
F I G . 31 is a photograph of the inside of the polymerization
reactor after completion of the polymerization reaction of
Comparative Example 2.
20 F I G . 32 is an SEM photograph of the ethylene polymer of
Comparative Example 3.
F I G . 33 is a photograph of the inside of the polymerization
reactor after completion of the polymerization reaction of
Comparative Example 3.
FIG. 34 is an SEM photograph of the ethylene polymer of
Comparative Example 4.
FIG. 35 is a photograph of the inside of the polymerization
reactor after completion of the polymerization reaction of
5 Comparative Example 4.
BEST MODE FOR CARRYING OUT THE INVENTION
[0022]
The method of production of ethylene-based polymer
10 particles according to the present invention, the ethylene-based
polymer particles obtained by this production method, and the
stretch-molded article manufactured from these ethylene-based
polymer particles are explained below in further detail. The
"ethylene-based polymer particles" of the present invention are
15 takentomeanpolymerparticleshavingethyleneas amaincomponent,
andthe "ethylene-basedpolymerparticles"includesbothethylene
homopolymer particles andethylene/a-olefin copolymerparticles.

The olefin polymerization catalyst used for the method of
20 production of ethylene-based polymer particles according to the
present invention is characterized by including:
(A) fine particles obtainedbya specificprocess andhaving
an average particle diameter greater than or equal to 1 nm and
less than or equal to 300 nm, and
(B) a transition metal compound represented in General
Formula (I) or General Formula (11) .
[0023]
The (A) and (B) components, as well as other components
capable of use as may be required, will be explained below in
detail.
[(A) Fine Particles Having an Average Particle Diameter Greater
than or Equal to 1 nm and Less than or Equal to 300 nm]
The fine particles used in the present invention and having
an average particle diameter greater than or equal to 1 nm and
less than or equal to 300 nmare obtainedby at least the following
two steps:
[0024]
(Step 1) a step of causing contact between a metal halide
and an alcohol in a hydrocarbon solvent, and
(Step 2) a step of causing contact between the component
obtained in (Step 1) and an organoaluminum compound and/or an
organoaluminumoxy compound.
The details of each step and the compounds used in each step
will be explained below.
Step 1
Step 1 is a step for causing contact between a metal halide
and an alcohol in a hydrocarbon solvent and forming an alcohol
complex of the metal halide in the liquid state.
I [0025]
Althoughnoparticularlimitationis placed on t h e r e a c t i o n
conditions of Step 1 as long as t h e s e r e a c t i o n c o n d i t i o n s a r e
normal f o r production of t h e metal h a l i d e i n t h e l i q u i d s t a t e ,
5 the r e a c t i o n is normally performed under heating a t atmospheric
pressure or e l e v a t e d p r e s s u r e . I f heating a t atmospheric
pressure i s u s e d , anytemperaturemaybe s e l e c t e d u p t o t h e b o i l i n g
pointoftheutilizedhydrocarbonsolvent. I f h e a t i n g a t elevated
pressure is used, t h e temperature may be s e l e c t e d a r b i t r a r i l y up
10 t o t h e b o i l i n g p o i n t o f t h e u t i l i z e d h y d r o c a r b o n s o l v e n t o r a l c o h o l
under elevated pressure.
[002 61
Themetal h a l i d e a n d t h e alcohol c a n b e b r o u g h t i n t o contact
i n t h e h y d r o c a r b o n s o l v e n t i n S t e p l b y n o r m a l s t i r r i n g andmixing.
15 Generally used and known a g i t a t o r s or t h e l i k e may be used as t h e
apparatus f o r s t i r r i n g .
Metal Halide
P r e f e r r e d examples of t h e metal h a l i d e used i n t h e present
i n v e n t i o n i n c l u d e i o n i c bonded compounds having a CdC12 type or
20 CdI2 type layered c r y s t a l s t r u c t u r e . S p e c i f i c examples of
compounds having a CdC12 type c r y s t a l s t r u c t u r e include CdC12,
MnC12, FeC12, CoC12, N i I 2 , N i C 1 2 , MgC12, ZnBr2, CrC13 or t h e l i k e .
S p e c i f i c examples of compounds having a Cd12 type c r y s t a l
s t r u c t u r e include CdBr2, FeBr2, CoBr2, N i B r 2 , Cd12, Mg12, Ca12, Zn12,
Pb12, Mn12, FeI2, CoI2, Mg(OH12, Ca(OH)2, Cd(OH)2, Mn(OH)2, Fe(OH)2,
Co(OH)2, N i (OH)2, ZrS4, SnS4, TiS4, PtS4 or t h e l i k e .
[0027]
Preferred compounds among such examples a r e CdBr2, FeBr2,
5 CoBr2, N i B r 2 , Cd12, Mg12, CaI2, ZnI2, PbI2, MnI2, Fe12, Co12, CdC12,
MnC12, FeC12, CoC12, N i 1 2 , NiC12, MgC12, ZnBr2. Further p r e f e r r e d
examples a r e MnC12, FeC12, CoC12, N i C 1 2 , and MgC12. MgC12 is most
p r e f e r r e d .
[0028]
10 Aslongastheionicbondedcompoundisincludedinthe f i n a l
c a t a l y s t , thereisnoneedtousetheionicbondedcompounditself.
Thus, during p r e p a r a t i o n of t h e c a t a l y s t , it is permissible t o
use compounds capable of forming t h e i o n i c bonded compound and
f i n a l l y t o cause t h e i o n i c bonded compound t o be present i n t h e
15 c a t a l y s t . That is t o say, it is permissible t o use a compound
t h a t has n e i t h e r a CdC12 type c r y s t a l s t r u c t u r e nor a Cd12 type
c r y s t a l s t r u c t u r e , during p r e p a r a t i o n of t h e c a t a l y s t t o cause
r e a c t i o n by contact t o g e t h e r of t h i s compound and a
halogen-containing compound or a hydroxyl-group containing
20 compound, and t o produce t h e i o n i c bonded compound f i n a l l y i n t h e
obtained c a t a l y s t .
[0029]
For example, i n t h e case of forming MgC12 or Mg12 and making
t h i s compound e x i s t among t h e f i n a l c a t a l y s t components, it is
possible to use magnesium compounds both having reducibility and
having no reducibility as raw material. Magnesium compounds
having reducibility are exemplified by the organomagnesium
compounds represented in following formula.
5 [0030]
XnMgR2-n
(in the formula; n satisfies 0 I n < 2; R is a hydrogen atom or
an alkyl group having 1 to 20 carbon atoms, an aryl group having
6 to 21 carbon atoms, or a cycloalkyl group having 5 to 20 carbon
10 atoms, where two R may be the same or different when n is 0; and
X is a halogen)
Specific examples of the organomagnesium compound having
reducibility include dialkyl magnesium compounds such as
dimethylmagnesium, diethylmagnesium, dipropylmagnesium,
15 dibutylmagnesium, diamylmagnesium, dihexylmagnesium,
didecylmagnesium, octylbutylmagnesium, ethylbutylmagnesium, and
the like; alkylmagnesiumhalides suchas ethylmagnesiumchloride,
propylmagnesium chloride, butylmagnesium chloride,
hexylmagnesium chloride, amylmagnesium chloride, and the like;
20 alkyl magnesium alkoxides such as butylethoxyrnagnesium,
ethylbutoxymagnesium, octylbutoxymagnesium, or the like; as well
as alkyl magnesium hydrides such as ethylmagnesium hydride,
propylmagnesium hydride, butylmagnesium hydride, and the like.
[0031]
Specific examples of the organomagnesium compound having
no reducibility include alkoxymagnesium halides such as
methoxymagnesium chloride, ethoxymagnesium chloride,
isopropoxymagnesium chloride, butoxymagnesium chloride,
5 octoxymagnesiumchloride, andthe like; aryloxymagnesiumhalides
such as phenoxymagnesium chloride, methylphenoxymagnesium
chloride, andthe like; alkoxyrnagnesiums suchas ethoxymagnesium,
isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium,
2-ethylhexoxymagnesium, and the like; aryloxymagnesiums such as
10 diphenoxymagnesium, methylphenoxymagnesium, and the like; and
carboxylic acid salts of magnesium such as magnesium laurate,
magnesium stearate, and the like.
[0032]
Other magnesium metal, magnesium hydride, or the like also
15 can be used. Such magnesium compounds having no reducibility may
be compounds derived fromthe aforementionedmagnesiumcompounds
having reducibility or may be compounds derived during the
preparation of the catalyst. In order to derive the magnesium
compoundhavingnoreducibilityfromthemagnesiumcompoundhaving
20 reducibility, for example, the magnesium compound having
reducibility may be contacted with a polysiloxane compound,
halogen-containing silane compound, halogen-containing aluminum
compound, ester, alcohol, halogen-containing compound, or a
compound having an OH group or an active carbon-oxygen bond.
@
[0033]
The magnesium compounds having reducibility and magnesium
compounds having no reducibility may form complex compounds or
double compounds together with organometallic compounds of other
5 metalssuchasaluminum, zinc, boron, beryllium, sodium, potassium,
andthe like, ormay bemixedwith these organometallic compounds.
Furthermore, the magnesium compound may be used singly or in
combination of two or more kinds. Moreover, the magnesium
compound may be used in the liquid state or solid state. When
10 the magnesiumcompound having reducibility or magnesium compound
having no reducibility is a solid, the magnesium compound is
preferably dissolved using the below described alcohol.
Alcohol
The alcohol used in the present invention is exemplified
15 by alcohols having 1 to 25 carbon atoms. Specific examples of
the alcohols include alcohols having 1 to 25 carbon atoms, such
as methanol, ethanol, propanol, butanol, pentanol, hexanol,
2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl
alcohol, 2-butyloctanol, 2-hexyldecanol, 2-hexyldodecanol,
20 2-octyldecanol, 2-octyldodecanol, isohexadecanol, isoeicosanol,
benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl
alcohol, isobutyl alcohol, and isopropylbenzyl alcohol;
halogen-containing alcohols having 1 to 25 carbon atoms, such as
trichloromethanol, trichloroethanol, and trichlorohexanol;
phenols having 6 to 25 carbon atoms and optionally having a lower
alkylgroup, suchas phenol, cresol, xylenol, ethyl phenol, propyl
phenol, nonyl phenol, cumyl phenol, and naphthol.
[0034]
5 Such alcohols may be used singly or in combination of two
or more kinds. From the below described standpoint, a mixture
of two kinds of alcohols is preferably used.
[0035]
The two kinds of alcohols are classified according to
10 differences of reactivity with the alcohol complex of the metal
halide in which the alcohol is included, and the below described
organoaluminum compound and/or organoaluminumoxy compound. The
following is inferred as the reason for preferred use of the
combination of such two types of alcohols.
15 [0036]
For the alcohol complex of the metal halide obtained from
the alcohol having high reactivity with the organoaluminum
compound and/or organoaluminumoxy compound, the alcohol is
extracted from the alcohol complex of the metal halide due to
20 contact and reaction with the organoaluminum compound and/or
organoaluminumoxycompound, anditispossibletorapidlygenerate
a parts that form the nuclei of the fine particle of metal halide.
[0037]
On the other hand, for the alcohol complex of the metal
* 23
halide obtained fromthe alcohol having relativelylowreactivity
with the organoaluminum compound and/or organoaluminumoxy
compound, after formation of the parts that form the nuclei of
the fine particles, the alcohol is extracted from the alcohol
5 complex of the metal halide, the metal halide precipitates to the
outside of the nuclei of the fine particles, and it is thought
that fine particles are formed that have an average particle
diameterasdefinedforthe (A) component ofthepresent invention.
[0038]
10 Itisthuspossibletoanticipateasmalldiameterandnarrow
particle size distribution for the fine particles that are the
(A) component of the present invention, and it may be assumed that
there will be little contamination of extremely fine particles,
suchasbyproduct particleshavingtheparticle size ofthenuclei.
15 [0039]
The below described ethylene-based polymer particles are
quite readily affected by the particle diameter of these fine
particles, and thus if the fine particles that are the (A)
component of the present invention are used as a constituent
20 element of the olefin polymerization catalyst, it is thought that
generation of irregularly shaped ethylene-based polymer
particles be difficult, and fouling of the reactor or the like
does not occur easily even when the polymer particles are
nano-sized.
*
[0040]
It is possible to assume that the differences in the
reactivityofthe alcohol withthe organoaluminumcompoundand/or
organoaluminumoxy compound are attributed to differences in the
5 molecular structure of the alcohol as represented in (i) to (iv) :
[0041]
(i) differences between linear and branching structures,
(ii) differences among aliphatic, alicyclic, and aromatic
structures,
10 (iii) differences in the number of carbon atoms, and
(iv) a combination of the (i) to (iii).
Among these differences, for example, if the (iii)
difference in the number of carbon atoms is indicated using the
number of carbon atoms of R where the alcohol is represented as
15 R-OH, it is possible to distinguish between alcohols having a
relatively low number of carbon atoms and alcohols having a
relatively large number of carbon atoms. In this case, the
alcohols having a relativelylownumber of carbon atoms generally
have high reactivity with the organoaluminum compound and/or
20 organoaluminumoxy compound. On the other hand, the alcohols
having a relatively large number of carbon atoms correspond to
alcohols having low reactivity with the organoaluminum compound
and/or organoaluminumoxy compound.
[0042]
25
According t o the c l a s s i f i c a t i o n based on the number of
carbon atoms, i n an embodiment, alcohols having a r e l a t i v e l y low
number of carbon atoms may be recognized as alcohols having a
r e l a t i v e l y large number of carbon atoms, depending on the kind
of the other alcohols. For example, i n the case of using
2-ethylhexanol, when2-octyldodecanolisusedastheotheralcohol,
the 2-ethylhexanol corresponds t o an alcohol having a r e l a t i v e l y
low number of carbon atoms. When isobutyl alcohol is used as the
otheralcohol,the2-ethylhexanolcorrespondstoanalcoholhaving
a r e l a t i v e l y large number of carbon atoms. Since t h i s
c l a s s i f i c a t i o n is focused j u s t on r e a c t i v i t y , no problems a r i s e
even i f a s i n g l e kind of alcohol is c l a s s i f i e d as e i t h e r
c l a s s i f i c a t i o n .
[0043]
Here, when the two kinds of alcohols are used i n a
combination, upon consideration of the e f f e c t s t h a t occur from
the standpoint o f t h e r e a c t i v i t y , t h e d i f f e r e n c e i n carbon number
between these two kinds of alcohols is preferably g r e a t e r than
or equal t o 4 .
[0044]
Specific examples of combinations of alcohols include a
combinationofanalcoholhaving2to12 carbonatoms andanalcohol
having13to25carbonatoms, acombinationoftwokindsofalcohols
having 2 t o 12 carbon atoms, or the l i k e .
C
[0045]
Here, the alcohol having 2 to 12 carbon atoms is preferably
an alcohol having 2 to 10 carbon atoms, and is particularly
preferably selected from ethanol, propanol, butanol, pentanol,
5 hexanol, 2-ethylhexanol, heptanol, and octanol.
[0046]
Moreover, the alcohol having 13 to 25 carbon atoms is
preferably an alcohol having 15 to 25 carbon atoms. Alcohols
having 16 to 25 carbon atoms are further preferred, and
10 particularlypreferredalcohols are selected from2-hexyldecanol,
2-hexyldodecanol, 2-octyldecanol, 2-octyldodecanol,
isohexadecanol, isoeicosanol, octadecyl alcohol, and oleyl
alcohol.
LO0471
When an alcohol having a relatively large number of carbon
atoms, suchas the alcoholhaving13to 25 carbon atoms, is present
in the olefin polymerization catalyst, it is possible to
anticipate that the ethylenepolymerizationreactionwillproceed
mildly and that localization of heat generation during the
20 polymerization will be suppressed. The suppression of
localization of heat generation during polymerization is thought
to be related to the suppression of entanglement of the generated
polymerchains, andas a result, performanceofthe stretch-molded
article, such as solid-phase stretch-molded article, can be
improved.
No particular limitation is placed on the amount of alcohol
used to make the metal halide in a liquid state as long as the
5 amount dissolves the metal halide. However, the amount of the
alcohol per 1 mol of metal halide is 0.1 to 50 mol, preferably
is 0.5 to 30 mol, more preferably is 1 to 20 mol, and further
preferably is 2 to 15 mol. When a mixture of two kinds of alcohol
are used as in the preferred embodiment, as long as the amount
10 of alcohol dissolves the metal halide, no particular limitation
is placedonthe ratioofthealcoholhavingarelativelylownumber
of carbon atoms and the ratio of the alcohol having a relatively
large number of carbon atoms. However, the lower limit of the
I ratio of the alcohol having a relatively large number of carbon
15 atoms is 10 mol%, preferably is 20 mol%, and further preferably
is 30mol%, and the upper limit ofthe ratio is 95mol%, preferably
is 90 mol%, and further preferably is 85 mol%.
Hydrocarbon solvent
No particular limitation is placed on the hydrocarbon
20 solvent used in the present invention. Specific examples include
aliphatic hydrocarbons such as hexane, heptane, octane, decane,
dodecane, kerosene, and the like; alicyclic hydrocarbons such as
cyclopentane, cyclohexane, methylcyclopentane, and the like;
aromatic hydrocarbons such as benzene, toluene, xylene, and the
like; halogenated hydrocarbons such as ethylene chloride,
chlorobenzene, dichloromethane, and the like; and a mixture
thereof.
[0049]
5 Of these, from the standpoints of solubility and reaction
temperature, use of decane, dodecane, toluene, xylene, and
chlorobenzene is preferred.
[0050]
No particular limitation is placed on the amount of the
10 h y d r o c a r b o n s o l v e n t u s e d t o m a k e t h e m e t a l h a l i d e i n a l i q u i d s t a t e
as long as the amount dissolves the metal halide. However, the
amount of the hydrocarbon solvent per 1 mol of the metal halide
is preferably 0.1 to 100 moll more preferably is 0.2 to 50 mol,
further preferably is 0.3 to 40 mol, and most preferably is 0.5
15 to 30 mol.
I
Step 2
In Step 2, the organoaluminum compound and/or
organoaluminumoxy compound are contacted with alcohol complex of
the metal halide in the liquid state obtained during Step 1, the
20 dissolved metal halide is precipitated out, and fine particles
are produced.
[0051]
Step 2 is performed under normal reaction conditions for
precipitation of a dissolved metal halide. However, this
precipitation is preferably performed at a temperature of -50 to
200°C, more preferably at a temperature of -20 to 150°C, and most
preferably at a temperature of 0 to 120'~.
[0052]
Moreover, in the Step 2, the organoaluminumcompoundand/or
organoaluminumoxy compound is addedto the solution while mixing
and stirring solution within a reactor. Stirring and mixing may
beperformedundernormalstirringconditions, althoughhighspeed
stirring-mixing may be required.
10 [0053]
The apparatus used for high-speed stirring is not
particularly limited as long as the apparatus is a general
commercial emulsifier or disperser, as exemplified by: batch
emulsifiers such as Ultra-Turrax (IKA Works), Polytron
15 (Kinematica, Inc. ) , TK Autohomomixer (Tokushu Kika Kogyo Co.,
Ltd.), National CookingMixer (Matsushita Electric Industrial Co.,
Ltd.), and the like; continuous emulsifiers such as Ebara Milder
(Ebara Corp.), TK Pipeline Homo Mixer, TK Homomic Line Flow
(Tokushu Kika Kogyo Co., Ltd.), Colloid Mill (Nippon Seiki Co.,
20 Ltd. ) , Thrasher, Trigonal Wet Pulverizer (Mitsui Miike Chemical
Engineering Machinery), Cavitron (Eurotech Company), Fine Flow
Mill (Pacific Machinery & Engineering Co., Ltd. ) , and the like;
batch or continuous dual-mode emulsifiers such as CLEARMIX (M
Technique Co., Ltd. ) , Filmix (Tokushu Kika Kogyo Co., Ltd. ) , and
t h e l i k e ; h i g h p r e s s u r e e m u l s i f i e r s s u c h a s M i c r o f l u i d i z e r (Mizuho
Industrial Co., Ltd.), Nanomaker, Nanomizer (Nanomizer Inc.), APV
Gaulin (Gaulin), and the like; membrane emulsifiers such as
Membrane Emulsifier (Reika Kogyo Co., Ltd.) and the like;
vibrating emulsifiers such as Vibromixer (Reika Kogyo Co., Ltd.)
and the like; and ultrasonic emulsifiers such as Ultrasonic
Homogenizer (Branson) andthe like; andthe like. Whenhigh speed
stirring-mixing is performed, the stirring speed is preferably
greater than or equal to 5,000 rpm.
Organoaluminum compound
The organoaluminum compound capable of use in the present
inventionis exemplifiedbythecompounds representedinfollowing
Formulae ( A - , (Al-2) , and (A1-3) .
[0054]
R~,A~x~(-A,1- 1 )
(in Formula (Al-1) , R~ is a hydrocarbon group having 1 to 12 carbon
atoms; X is a halogen atom or hydrogen atom; and n ranges from
1 to 3)
Examplesofthehydrocarbongrouphaving1to12 carbonatoms
include alkyl groups, cycloalkyl groups, and aryl groups.
Specific examples of the hydrocarbon group include the methyl
group, ethyl group, n-propyl group, isopropyl group, isobutyl
group, pentyl group, hexylgroup, octylgroup, cyclopentyl group,
cyclohexyl group, phenyl group, tolyl group, or the like.
e
[0055]
Specific examples of this type of organoaluminum compound
include following compounds: trialkylaluminum compounds such as
trimethylaluminum, triethylaluminum, triisopropylaluminum,
5 triisobutylaluminum, trioctylaluminum,
tri-2-ethylhexylaluminum, and the like; alkenyl aluminum
compounds suchasisoprenylaluminumandthelike; dialkylaluminum
halides such as dimethylaluminum chloride, diethylaluminum
chloride, diisopropylaluminum chloride, diisobutylaluminum
10 chloride, dimethylaluminum bromide, and the like; alkyl aluminum
sesquihalides such as methylaluminum sesquichloride,
ethylaluminumsesquichloride, isopropylaluminumsesquichloride,
butylaluminum sesquichloride, ethylaluminum sesquibromide, and
the like; alkyl aluminum dihalides such as methylaluminum
15 dichloride, ethylaluminum dichloride, isopropylaluminum
dichloride, ethylaluminum dibromide, and the like; and alkyl
aluminum hydrides such as diethylaluminum hydrides,
diisobutylaluminum hydrides, or the like.
[0056]
20 Moreover, an organoaluminum compound represented in
following formula may be used.
, [0057]
Ran~1y3-(,A l-2)
(in Formula (Al-2), Ra has the same meaning as that of Formula
(Al-1) ; Y is an -ORb group, -0siRC3g roup, - 0 ~ 1g~ro~up2, - N R ~gr~ou p,
- s ~ gRro~up~, or -N ( R ~ ) Ag~roRu~p;~ n is 1 to 2; R ~ ,RC , R~ and Rh
are amethyl group, ethyl group, isopropylgroup, isobutylgroup,
cyclohexyl group, phenyl group, or the like; Re is a hydrogen,
5 methyl group, ethyl group, isopropyl group, phenyl group,
trimethylsilyl group, or the like; and Rf and Rg are a methyl group,
ethyl group, or the like.)
Specific examples of the organoaluminum compound
represented in Formula (Al-2) include following compounds:
(i) compounds represented by formula : Ran~(lO Rb)3- nr as
exemplified by
alkylaluminumalkoxides suchas dimethylaluminummethoxide,
diethylaluminum ethoxide, diisobutylaluminum methoxide,
diethylaluminum-2-ethylhexoxide, and the like;
15 (ii) compounds represented by formula: Ran~(lO SiRC33)- nf as
exemplified by
Et2A1 (OSiMe3), (iso-Bu)2 Al (OSiMe3), (iso-Bu)2 Al (OSiEt3) or
the like;
(iii) compounds represented by formula: Ran~(l0 ~ 1 ~3-~nr2 a)s
20 exemplified by
Et2A10A1Et2, (iso-Bu)2 AlOA1 (iso-Bu)2 or the like;
(iv) compounds represented by formula: RanA1( NRe23)- nr as
exemplified by
(iso-Bu)2 AlN (Me3Si)2 or the like;
(v) compounds represented by formula: R~,A(~ ~ i ~3-,~, 3a)s
exemplified by
(i~o-Bu)~AlSiMoer ~t he like; and
(vi)c ompounds represented by formula: Ran~[lN (Rq)- A~R~3-znr]
as exemplified by
Et2AlN (Me) -A1Et2, (iso-Bu) zAIN (Et)Al (iso-Bu) 2 or the like.
[0058]
It is furtherpossibletouse as the organoaluminumcompound
10 a compound represented in following Formula (Al-3), which is an
alkylcomplex compound of aluminum and a Group I metal.
[0059]
M'A~R'~ (Al-3)
(in Formula (Al-3), M' is Li, Na, or K; and R~ is a hydrocarbon
15 group having 1 to 15 carbon atoms)
Examples thereof include LiAl (C2H54) and LiAl (C7H154) o r the
like.
[0060]
Among the aforementioned organoaluminum compounds,
20 trimethylaluminum, triethylaluminum, triisobutylaluminum,
trihexylaluminum, trioctylaluminum, diethylaluminum chloride,
ethylaluminum sesquichloride, ethylaluminum dichloride, and
diisobutylaluminum hydride are particularly preferred.
[0061]
During precipitation of the dissolved metal halide and
production of the fine particles, the utilized amount of the
organoaluminumcompoundper1molofthemetalhalideispreferably
0.lto 50mo1, furtherpreferablyis 0.2 to 30mo1, more preferably
is 0.5 to 20 molt and most preferably is 1.0 to 10 mol.
Organoaluminumoxy Compound
The organoaluminumoxy compound used in the present
invention may be any previously known aluminoxane, or may be a
benzene-insoluble organoaluminumoxy compound such as that
disclosed in Japanese H2-78687. Specific examples of the
organoaluminumoxy compound include methylaluminoxane,
ethylaluminoxane, isobutylaluminoxane, or the like.
[0062]
For example, conventional aluminoxane can be prepared by
the following processes, and is generally obtained as a solution
in a hydrocarbon solvent.
(1) An organoaluminum compound such as trialkylaluminum is
addedto a hydrocarbonmedium suspension of a compound containing
absorbedwater or a saltcontainingwaterofcrystallization, e.g.,
magnesium chloride hydrate, copper sulfate hydrate, aluminum
sulfatehydrate, nickelsulfatehydrateorcerous chloridehydrate,
to allow the organoaluminum compound to react with the absorbed
water or the water of crystallization.
(2) Water, ice or water vapor is allowed to react directly
with an organoaluminum compound such as trialkylaluminum
medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) An organotin oxide such as dimethyltin oxide or
dibutyltin oxide allowed react with organoaluminum
compound such as trialkylaluminum in a medium such as decane,
benzene or toluene.
[0063]
The aluminoxane may contain a small amount of an
organometallic component. Further, it is possible that the
solvent or the unreacted organoaluminumcompoundis distilled off
from the recovered solution of aluminoxane and the remainder is
redissolved in a solvent or suspended in a poor solvent for
aluminoxane.
[0064]
Specific examples of the organoaluminum compounds used in
the preparation of aluminoxanes include the organoaluminum
compounds described above for the
[0065]
Of these, trialkylaluminums a
preferable, and trimethylaluminum
[0066]
organoaluminum compounds.
.ndtricycloalkylaluminums are
is particularly preferable.
The organoaluminumcompounds areusedsingly, or twoormore
kinds are used in combination.
[0067]
Examples of the solvents used in the preparation of
aluminoxanes include aromatic hydrocarbons such as benzene,
toluene, xylene, cumene and cymene; aliphatic hydrocarbons such
aspentane, hexane, heptane, octane, decane, dodecane, hexadecane
5 and octadecane; alicyclic hydrocarbons such as cyclopentane,
cyclohexane, cyclooctane and methylcyclopentane; petroleum
fractions such as gasoline, kerosine and light oil; and halides
such as chlorides and bromides of these aromatic, aliphatic and
alicyclic hydrocarbons. Ethers such as ethyl ether and
10 tetrahydrofuran are also employable. Of the solvents, the
aromatic hydrocarbons or the aliphatic hydrocarbons are
particularly preferable.
[0068]
In the benzene-insoluble organoaluminumoxy compound used
15 in the present invention, the content of the A1 component that
is soluble in benzene at 60°c is usually less than or equal to
lo%, preferably is less than or equal to 5%, and particularly
preferably is less than or equal to 2%, in terms of A1 atom. That
is, the benzene-insoluble organoaluminumoxy compound is
20 preferably insoluble or hardly soluble in benzene.
[0069]
The organoaluminumoxy compound employable in the present
invention is, for example, an organoaluminumoxy compound
containing boron and represented in following General Formula
[0071]
5 (in General Formula (111) , R2' is a hydrocarbon group having 1 to
10 carbon atoms; four R~~ groups may be the same or different and
are a hydrogen atom, halogen atom, or hydrocarbon group having
1 to 10 carbon atoms)
The boron-containing organoaluminumoxy compounds
10 represented by General Formula (111) can be prepared by allowing
analkylboronicacidrepresentedbyfollowingGeneralFormula (IV)
to react with an organoaluminum compound under an inert gas
atmosphere in an inert solvent for 1 minute to 24 hours at a
temperature of - 8 0 " ~ to room temperature.
15 [0072]
R Z 2 - ~(O H) 2 . . . (IV)
(in General Formula (IV), RZ2 is the same group as R~~ in General
Formula (111) )
Specific examples ofthe alkylboronic acids represented in
20 General Formula (IV) include methylboronic acid, ethylboronic
acid, isopropylboronic acid, n-propylboronic acid,
n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid,
cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic
acid, pentafluorophenylboronic acid and
3,5-bis (trif luoromethyl) phenylboronic acid. Of these,
methylboronic acid, n-butylboronic acid, isobutylboronic acid,
5 3,5-difluorophenylboronic acid and pentafluorophenylboronic
acid are preferable. These are employed singly or in combination
of two or more kinds.
LO0731
Specific examples of the organoaluminum compounds to be
10 reacted with the alkylboronic acids include the organoaluminum
compounds described above for the organoaluminum compounds. The
organoaluminum compound is preferably trialkyl aluminum or
tricycloalkyl aluminum, and particularly preferably is
trimethylaluminum, triethylaluminum, or triisobutylaluminum.
15 These are employed singly or in combination of two or more kinds.
[0074]
The organoaluminumoxy compounds mentioned above are used
singly, or two or more kinds are used in combination.
[0075]
During precipitation of the dissolved metal halide and
production of the fine particles, the utilized amount of the
organoaluminumoxy compound per 1 mol of the metal halide is
preferably 0.1to 50 mol, further preferably is 0.2 to 30 mol,
more preferably is 0.5 to 20 mol, and most preferably is 1.0 to
10 mol.
[0076]
Furthermore, the amount of the organoaluminumoxy compound
used when causing p r e c i p i t a t i o n of the metal h a l i d e is a small
5 amount i n comparison t o the amount of organoaluminumoxy compound
used as a co-catalyst as described i n Patent Document 1.
Fine p a r t i c l e s
The f i n e p a r t i c l e s having undergone a t l e a s t the Step 1 and
Step 2 have an average p a r t i c l e diameter, as measured by the
10 dynamic l i g h t s c a t t e r i n g method, of greater than or equal t o 1
nm and l e s s than or equal t o 300 nm, preferably is g r e a t e r than
or equal t o 1 nm and l e s s than or equal t o 250 nm, more preferably
i s greater than or equal t o 1 nm and l e s s than or equal t o 200
nm, f u r t h e r preferably is g r e a t e r than or equal t o 1 nm and l e s s
15 than or equal t o 150 nm, yet f u r t h e r preferably is g r e a t e r than
o r e q u a l t o 1 n m a n d l e s s t h a n o r e q u a l t o 1 0 0 n m , andmostpreferably
is greater than or equal t o 1 nm and l e s s than or equal t o 50 nm.
[0077]
Reasonsthatmaybe considered f o r t h e use of f i n e p a r t i c l e s
20 having t h i s type of s i z e a r e l i s t e d below. Due t o t h e s p e c i f i c
surface area of the support becoming large by using t h e f i n e
p a r t i c l e s a s a support f o r t h e c a t a l y s t , when the below described
(B) t r a n s i t i o n metal compound is supported, the distance between
t h e a c t i v e s i t e s o f t h e generatedethylenepolymerizationbecomes
1
I long. When t h e d i s t a n c e b e t w e e n a c t i v e s i t e s b e c o m e s l o n g i n t h i s
manner, the generated heat around the a c t i v e s i t e s decreases, the
c r y s t a l l i z a t i o n temperature of the generated ethylene-based
polymer becomes low, and the l a m e l l a r t h i c k n e s s decreases.
I
i 5 Moreover, it becomes possible t o decrease the entanglement of the
polymer chains of the generated ethylene-based polymer. Due t o
such c h a r a c t e r i s t i c s , when the f i n e p a r t i c l e s of the present
invention are used as a c a t a l y s t support, the c r y s t a l portion of
the obtained ethylene-basedpolymerparticles r e a d i l y b r e a k s down
10 during s t r e t c h i n g , and thus s t r e t c h a b i l i t y becomes high. As a
r e s u l t , t h e degree of o r i e n t a t i o n becomes high, and it is
a n t i c i p a t e d t h a t high strength w i l l be r e a l i z e d .
[0078]
By using f i n e p a r t i c l e s having t h i s type of s i z e as the
15 c a t a l y s t support, due t o s p e c i f i c s u r f a c e a r e a of the support
becoming high i n the above described manner, i f distance between
a c t i v e s i t e s is s e c u r e d i n t h e samemanner as f o r t h e conventional
support, it is p o s s i b l e t o i n c r e a s e t h e amount o f t r a n s i t i o n m e t a l
compoundsupportedpersupportparticleandtoincreasetheolefin
20 p o l y m e r i z a t i o n a c t i v i t y p e r u n i t of c a t a l y s t m a s s . Moreover, the
monomer d i f f u s e s well during the polymerization. Moreover, i f
the below described (C) compound forming an ion p a i r by reaction
with t h e t r a n s i t i o n metal compound or the (D) organoaluminumoxy
compound is used as a component of the o l e f i n polymerization
catalyst, active sites are thought to be formed efficiently due
to high probability of contact between these compounds and the
(B) transition metal compound supported on the support. Based
on such characteristics, it is anticipated to be possible to
5 improve catalytic activity by using the fine particles of the
present invention as the support for the catalyst.
[ (B) Transition Metal Compound]
As long as it is possible to realize the below described
intrinsic viscosity, crystallinity, or the like of the
10 ethylene-based polymer particles, the transition metal compound
usedinthe present inventionmaybe any transitionmetal compound
without limitation, such as a known metallocene compound or a
so-called post-metallocene or the like specific
organo-transition metal complex compound.
15 [0079]
The organo-transition metal complex described in Patent
Document2 (i.e. so-calledorgano-transitionmetal complexhaving
a phenoxy-imine ligand) is preferred as the (B) transition metal
compound included in the olefin polymerization catalyst in the
20 present invention. Specifically, preferred embodiments of the
organo-transition metal complex are exemplified by
organo-transition metal complexes having a structural formula
such as that represented in following General Formula (I).
[0080]
[0081]
InGeneral Formula (I), Mis atransitionmetal atomof Group
4 or 5 in the periodic table and preferably is a transition metal
5 atom of Group 4. Specific examples of the transition metal atom
are titanium, zirconium, hafnium, vanadium, niobium, tantalum,
or the like. Furtherpreferredexamples aretitanium, zirconium,
and hafnium. Particularly preferred examples are titanium and
zirconium.
10 [0082]
The dotted line between N and M in General Formula (I)
indicates that N is generally coordinated on M, although
coordination is optional in the present invention.
[0083]
In General Formula (I), m is an integer from 1 to 4,
preferably an integer from 2 to 4, and further preferably 2.
[0084]
In General Formula (I), R1 to R5 may be the same or different
and are a hydrogen atom, halogen atom, hydrocarbon group,
20 heterocyclic compound residue, oxygen-containing group,
nitrogen-containing group I boron-containing group r
I sulfur-containing group, phosphorous-containing group,
silicon-containing group, germanium-containing group, or
tin-containing group, where two or more such groups may be bonded
together t o form a ring.
5 [0085]
Examples of the halogen atom include f l u o r i n e , chlorine,
bromine, and iodine.
[0086]
The hydrocarbon group is exemplifiedby l i n e a r o r branched
10 a l i p h a t i c hydrocarbon groups having 1 t o 30 carbon atoms, c y c l i c
hydrocarbon groups having 3 t o 30 carbon atoms, and aromatic
hydrocarbongroupshaving 6 t o 30 carbonatoms. Specificexamples
include: l i n e a r or branched alkyl groups having 1 t o 30 carbon
atoms, preferably having 1 t o 20 carbon atoms, and f u r t h e r
15 preferably having 1 t o 10 carbon atoms, such as a methyl group,
ethyl group, n-propyl group, isopropyl group, n-butyl group,
isobutylgroup, sec-butylgroup, t-butylgroup, neopentylgroup,
n-hexyl group and t h e l i k e ;
l i n e a r o r b r a n c h e d a l k e n y l g r o u p s h a v i n g 2 t o 30 carbonatoms
20 and preferably having 2 t o 20 carbon atoms, such as a vinyl group,
a l l y 1 group, isopropenyl group, and t h e l i k e ;
l i n e a r o r b r a n c h e d a l k y n y l g r o u p s h a v i n g 2 t o 3 0 carbonatoms,
preferably having 2 t o 20 carbon atoms, and f u r t h e r preferably
having 2 t o 10 carbon atoms, such as an ethynyl group, propargyl
a!
group, and t h e l i k e ;
c y c l i c s a t u r a t e d hydrocarbon groups having 3 t o 30 carbon
atoms, preferably having 3 t o 20 carbon atoms, and f u r t h e r
preferablyhaving 3 t o 1 0 carbonatoms, suchas acyclopropylgroup,
5 cyclobutyl group, cyclopentyl group, cyclohexyl group,
cycloheptyl group, adamantyl group, and t h e l i k e ;
cyclicunsaturatedhydrocarbongroups having 5 t o 30 carbon
atoms, such as a cyclopentadienylgroup, indenylgroup, fluorenyl
group, and the like;
10 a r y l groups having 6 t o 30 carbon atoms, preferably having
6 t o 20 carbon atoms, and f u r t h e r preferably having 6 t o 10 carbon
atoms, such as a phenyl group, naphthyl group, biphenyl group,
terphenyl group, phenanthryl group, anthracenyl group, and the
l i k e ; and
15 a l k y l - s u b s t i t u t e d a r y l groups, such as a t o l y l group,
iso-propylphenyl group, t-butylphenyl group, dimethylphenyl
group, di-t-butylphenyl group, and the l i k e .
[0087]
In thehydrocarbongroup, ahydrogenatommaybe s u b s t i t u t e d
20 with halogen atoms, as exemplified by halogenated hydrocarbon
groups o f 1 to30 carbonatoms, a n d p r e f e r a b l y l t o 20 carbonatoms,
such as a trifluoromethyl group, pentafluorophenyl group,
chlorophenyl group, and the l i k e .
[0088]
The hydrocarbon groupmay also be substitutedwith another
hydrocarbon group. Examples of such hydrocarbon groups
substitutedbyahydrocarbongroupinclude aryl-substitutedalkyl
groups such as the benzyl group, cumyl group, and the like.
5 [0089]
The hydrocarbon groupmay optionally include: heterocyclic
compound residues;
oxygen-containing groups such as an alkoxy group, aryloxy
group, ester group, ether group, acyl group, carboxyl group,
10 carbonate group, hydroxy group, peroxy group, carboxylic acid
anhydride group, and the like;
nitrogen-containing groups such as an amino group, imino
group, amidegroup, imidegroup, hydrazinogroup, hydrazonogroup,
nitro group, nitroso group, cyano group, isocyano group, cyanic
15 acid ester group, amidino group, diazo group, ammonium salts of
amino group, and the like;
boron-containing groups such as a boranediyl group,
boranetriyl group, diboranyl group, and the like;
sulfur-containing groups such as a mercapto group,
20 thioester group, dithioester group, alkylthio group, arylthio
group, thioacyl group, thioether group, thiocyanic acid ester
group, isothiocyanic acid ester group, sulfonic ester group,
sulfonic amide group, thiocarboxyl group, dithiocarboxyl group,
sulfo group, sulfonyl group, sulfinyl group, sulfenyl group, and
the like;
phosphorus-containing groups such as a phosphide group,
phosphorylgroup, thiophosphorylgroup, phosphato group, and the
like;
silicon-containing groups; germanium-containing groups;
and tin-containing groups.
[0090]
Examples of the heterocyclic compound residue include
residues of nitrogen-containing compounds such as pyrrole,
10 pyridine, pyrimidine, quinoline and triazine, oxygen-containing
compounds suchas furanandpyran, andsulfur-containingcompounds
suchasthiophene; andgroupsinwhichtheseheterocycliccompound
residues are further substituted with substituents such as alkyl
groups and alkoxy groups having 1 to 30 carbon atoms, and
15 preferably 1 to 20 carbon atoms.
[0091]
Examples of the silicon-containing groups include a silyl
group, siloxy group, hydrocarbon-substituted silyl groups,
hydrocarbon-substituted siloxy groups, and the like. Further
20 specific examples include a methylsilyl group, dimethylsilyl
group, trimethylsilyl group, ethylsilyl group, diethylsilyl
group, triethylsilyl group, diphenylmethylsilyl group,
triphenylsilyl group I dimethylphenylsilyl group,
dimethyl-t-butylsilyl group, dimethyl(pentafluorophenyl)silyl
group, and the like. Preferred groups among these examples
include the methylsilyl group, dimethylsilyl group,
trimethylsilyl group, ethylsilyl group, diethylsilyl group,
triethylsilyl group, dimethylphenylsilyl group, triphenylsilyl
5 group, and the like. Particularly preferred groups among these
examples include the trimethylsilyl group, triethylsilyl group,
triphenylsilyl group, and dimethylphenylsilyl group. The
trimethylsiloxygrouporthelikemaybe exemplifiedas a specific
example of the above-described hydrocarbon-substituted siloxy
10 group.
[0092]
The germanium-containing groups and the tin-containing
groups include the above-mentioned silicon-containing groups in
which silicon is replaced with germanium or tin, respectively.
15 [0093]
Among the groups optionally included in the hydrocarbon
group,
specific examples of the alkoxy group include a methoxy
group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy
20 group, isobutoxy group, t-butoxy group, or the like.
Specific examples of the aryloxy groups include a phenoxy
group, 2,6-dimethylphenoxy group, 2,4,6-trimethylphenoxy group,
or the like.
Specific examples of the ester groups include an acetyloxy
48
group, benzoyloxy group, methoxycarbonyl group, phenoxycarbonyl
group, p-chlorophenoxycarbonyl group, or the like.
Specificexamples ofthe acylgroupsinclude a formylgroup,
acyl group, benzoyl group, p-chlorobenzoyl group,
5 p-methoxybenzoyl group, or the like.
Specificexamplesoftheaminogroupincludeadimethylamino
group, ethylmethylamino group, diphenylamino group, or the like.
Specific examples of the imino group include a methylimino
group, ethylimino group, propylimino group, butylimino group,
10 phenylimino group, or the like.
Specific examples of the amide group include an acetamide
group, N-methylacetamide group, N-methylbenzamide group, or the
like.
Specific examples of the imide group include an acetimide
15 group, benzimide group, or the like.
Specific examples of the thioester group include an
acetylthio group, benzoylthio group, methylthiocarbonyl group,
phenylthiocarbonyl group, or the like.
Specific examples of the alkylthio group include a
20 methylthio group, ethylthio group, or the like.
Specificexamples ofthe arylthiogroupinclude aphenylthio
group, methylphenylthio group, naphthylthio group, or the like.
Specific examples of the sulfoester group include a methyl
sulfonate group, ethyl sulfonate group, phenyl sulfonate group,
o r t h e l i k e .
S p e c i f i c examples of t h e sulfonamide group include a
phenylsulfonamide group, N-methylsulfonamide group,
N-methyl-p-toluenesulfonamide group, or t h e l i k e .
5 [0094]
P a r t i c u l a r l y p r e f e r r e d examples of the hydrocarbon group
are: l i n e a r or branched a l k y l groups having 1 t o 30 carbon atoms,
p r e f e r a b l y 1 t o 20 carbon atoms, such as a methyl group, e t h y l
group, n-propyl group, isopropyl group, n-butyl group, i s o b u t y l
10 group, sec-butyl group, t-butyl group, neopentyl group, n-hexyl
group, and the l i k e ;
a r y l groups having 6 t o 30 carbon atoms, p r e f e r a b l y 6 t o
20 carbon atoms, such as a phenyl group, naphthyl group, biphenyl
group, terphenylgroup, phenanthrylgroup, anthracenylgroup, and
15 t h e l i k e ; and
a s u b s t i t u t e d a r y l group where these a r y l groups a r e
s u b s t i t u t e d by 1 t o 5 s u b s t i t u e n t s such as a halogen atom, a l k y l
group or alkoxy group having 1 t o 30 carbon atom, p r e f e r a b l y 1
t o 2 0 carbonatom, arylgrouporaryloxygrouphaving 6 t o 30 carbon
20 atoms, p r e f e r a b l y 6 t o 20 carbon atoms, and the l i k e .
[0095]
In the aforementioned manner, R' t o R' may be a h e t e r o c y c l i c
compound residue, oxygen-containing group, nitrogen-containing
group, boron-containing group, s u l f u r - c o n t a i n i n g group,
phosphorous-containing group, silicon-containing group,
germanium-containing group, or tin-containing group. However,
examples of these groups are the same as those mentioned in the
above description of the hydrocarbon groups.
5 [0096]
From the standpoint of providing a high molecular weight
ethylene-based polymer and from the standpoint of olefin
polymerization catalytic activity, among R' to R5 of General
Formula (I), R1 is preferably a group selected from linear or branch
10 hydrocarbon groups having 1 to 20 carbon atoms, alicyclic
hydrocarbon groups having 3 to 20 carbon atoms, and aromatic
hydrocarbon groups having 6 to 20 carbon atoms.
[0097]
In General Formula (I), R6 is selected from a hydrogen atom,
15 hydrocarbon groups having 1 to 4 carbon atoms and composed of only
primary or secondary carbon atoms, aliphatic hydrocarbon groups
having at least 4 carbon atoms, aryl group-substituted alkyl
groups, monocyclic or bicyclic alicyclic hydrocarbon groups,
aromatic hydrocarbon groups, and halogen atoms. Among these
20 groups, from the standpoints of olefin polymerization catalytic
activity, providinga highmolecularweightethylenepolymer, and
hydrogen tolerance during polymerization, R~ is preferably
selected from aliphatic hydrocarbon groups having at least 4
carbon atoms, aryl-substituted alkyl groups, monocyclic or
bicyclic alicyclic hydrocarbon groups, and aromatic hydrocarbon
groups. Further preferred examples of R~ are branched hydrocarbon
groups suchas at-butylgroupandthelike; aryl-substitutedalkyl
groups suchasabenzylgroup, 1-methyl-1-phenylethylgroup (cumyl
5 group), 1-methyl-1,l-diphenylethylgroup, l,l,l-triphenylmethyl
group (trityl group), and the like; and alicyclic hydrocarbon
groups having an alicyclic or multicyclic structure and having
6tol5 carbonatoms suchas acyclohexylgrouphavingahydrocarbon
group at 1-position, norbornyl group, adamantyl group, and
10 tetracyclododecyl group, or the like.
[0098]
In General Formula (I), n is a number that satisfies the
valance number of M.
In General Formula (I), X is a hydrogen atom, halogen atom,
15 hydrocarbon group, oxygen-containing group, sulfur-containing
group, nitrogen-containing group, boron-containing group,
aluminum-containing group, phosphorous-containing group,
halogen-containing group, heterocyclic compound residue,
silicon-containing group, germanium-containing group or
20 tin-containing group. When n is greater than or equal to 2,
multiple groups indicated by X may be the same or different, and
the multiple groups indicated by X may be bonded together to form
a ring.
[0099]
The halogen atom, hydrocarbon group, heterocyclic compound
residue, oxygen-containing group, nitrogen-containing group,
boron-containing 9rOUPt sulfur-containing group,
phosphorous-containing group, silicon-containing group,
5 germanium-containinggroup, andtin-containing group ofxarethe
same as those cited in the description of R' to R ~ . Among these
examples, halogen atoms and hydrocarbon groups are preferred.
In the present invention, the transition metal compound
10 represented in General Formula (I) may be produced without
limitation by the production method described in the Patent
Document 3.
Moreover, the metallocene type compounds represented in
15 following General Formula (11) are cited as the transition metal
compound included in the olefin polymerization catalyst of the
present invention.
53
In General Formula (11), M is titanium, zirconium, or
hafnium.
[0104]
In General Formula (11), R1' to R'' may be the same or
5 different andare ahydrogenatom, halogenatom, hydrocarbongroup,
heterocyclic compound residue, oxygen-containing group,
nitrogen-containing group, boron-containing group,
sulfur-containing group, phosphorous-containing group,
silicon-containing group, germanium-containing group, or
10 tin-containing group, where two or more adjacent groups may be
optionally bonded together to form a ring.
[0105]
The halogen atom, hydrocarbon group, heterocyclic compound
residue, oxygen-containing group, nitrogen-containing group,
15 boron-containing group I sulfur-containing group,
phosphorous-containing group, silicon-containing group,
germanium-containing group, or tin-containing group of R" to R1'
are the same as those cited in the description of R' to R~ of General
Formula (I).
20 [0106]
In General Formula (11) , X' and x2 may be the same or different
and are a hydrocarbon group, oxygen-containing group,
sulfur-containinggroup, silicon-containinggroup, hydrogenatom,
or halogen atom.
In General Formula (11) , Y is a divalent hydrocarbon group,
divalent halogenated hydrocarbon group, divalent
silicon-containing group, divalent germanium-containing group,
5 divalent tin-containing group, -0-, -CO-, -S-, -SO-, -SOz-, -Ge-,
-Sn-, -NR-, -P (R) -, -P (0) (R) -, -BR-, or -AlR- [where R may be the
sameordifferentandisahydrogenatom, halogenatom, hydrocarbon
group, halogenated hydrocarbon group, or alkoxy group]. The
hydrocarbon group, oxygen-containing group, sulfur-containing
10 group, silicon-containing group, and halogen atom of Y are the
s a m e a s t h o s e c i t e d i n t h e d e s c r i p t i o n o f ~ 1 t o ~ 5 ~ f ~ e n e r a l ~ o r m u l a
(1).
[0108]
Preferred examples of the metallocene type compound are
15 compoundshavingthe structures describedinW001/027124 pamphlet,
W02004/029062 pamphlet, or the like.
[0109]
Of these, examples of metallocene type compounds that can
be particularly preferably used in the present invention include
20 diphenylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluoreny
1) zirconium dichloride,
diphenylmethylene(cyclopentadienyl) (3,6-di-tert-butylfluoreny
1) zirconium dichloride,
diphenylmethylene(cyclopentadienyl) (octamethyloctahydrodibenz
ofluorenyl) zirconium dichloride,
di(p-tolyl)methylene(cyclopentadienyl) (2,7-di-tert-butylfluor
enyl) zirconium dichloride,
di (p-tolyl)m ethylene (cyclopentadienyl)( 3,6-di-tert-butylfl uor
5 enyl) zirconium dichloride,
di (p-tolyl)m ethylene (cyclopentadienyl)
(octamethyloctahydrodibenzofluorenyl) zirconium dichloride,
di(p-chlorophenyl)methy1ene(cyclopentadienyl)(3,6-di-tert-but
ylfluorenyl) zirconium dichloride,
10 di(p-chlorophenyl)methylene(cyclopentadienyl)
(octamethyloctahydrodibenzof1uorenyl) zirconium dichloride, or
the like.
[OllO]
Compounds where "zirconium" is replaced with "hafnium" or
15 "titanium" in the aforementioned compounds and compounds where
"cyclopentadienyl" is replaced with
"3-tert-b~tyl-5-methyl-cyclopentadienyl,~'
"3,5-dimethyl-cyclopentadienyl,"
"3-tert-butyl-cyclopentadienyl," "3-methyl-cyclopentadienyl,"
20 or the like are cited as preferred examples.
[Other Components Capable of Use in the Olefin Polymerization
Catalyst]
The olefin polymerization catalyst used in the method of
production of ethylene-based polymer particles of the present
invention contains the aforementioned (A) and (B) components as
essential components.
[Olll]
In addition to the (A) and (B) components, other components
5 may be added and used in the olefin polymerization catalyst with
the object of adjusting physical properties of the obtained
ethylene-based polymer particles and of performing this method
of production of the ethylene-based polymer particles with high
catalytic activity.
10 [0112]
Aslongasperformanceoftheolefinpolymerizationcatalyst
includingthe (A) and (B) componentsisnotimpaired, noparticular
limitation is placedon suchother components. Typical other such
components capable of use are: (C) compounds forming an ion pair
15 by reaction with the (B) component, and (D) organoaluminumoxy
compounds, and these components will be explained below.
[(C): Compounds Forming an Ion Pair by Reaction with the (B)
Component]
The (C) compound forming the ion pair by reaction with the
20 (B) component and capable of use as a component of the olefin
polymerization catalyst of the present invention is exemplified
by organoaluminum compounds, halogenated boron compounds,
halogenatedphosphorous compounds, halogenatedsulfurcompounds,
halogenated titanium compounds, halogenated silane compounds,
halogenated germanium compounds, halogenated tin compounds, or
the like.
[0113]
Of these, preferred organoaluminum compounds may be
5 exemplified by the aforementioned organoaluminum compounds used
in the production of the (A) fine particles.
[0114]
Specificexample compounds for use as the halogenatedboron
compounds, halogenatedphosphorous compounds, halogenatedsulfur
10 compounds, halogenated titanium compounds, halogenated silane
compounds, halogenated germanium compounds, halogenated tin
compounds are listed below.
[0115]
Halogenated boron compounds such as trifluoroboron,
15 trichloroboron, tribromoboron, and the like;
halogenated phosphorous compounds such as phosphorous
trichloride, phosphorous tribromide, phosphorous triiodide,
phosphorous pentachloride, phosphorous pentabromide,
phosphorous oxychloride, phosphorous oxybromide,
20 methyldichlorophosphine, ethyldichlorophosphine,
propyldichlorophosphine, butyldichlorophosphine,
cyclohexyldichlorophosphine, phenyldichlorophosphine,
methyldichlorophosphine oxide, ethyldichlorophosphine oxide,
butyldichlorophosphineoxide, cyclohexyldichlorophosphineoxide,
phenyldichlorophosphine oxide, methylphenylchlorophosphine
oxide, dibromotriphenylphosphorane, tetraethylphosphonium
chloride, dimethyldiphenylphosphonium iodide,
ethyltriphenylphosphonium chloride, allyltriphenylphosphonium
5 chloride, benzyltriphenylphosphonium chloride,
allyltriphenylphosphonium bromide, butyltriphenylphosphonium
bromide, benzyltriphenylphosphonium bromide, and the like;
halogenated sulfur compounds such as sulfur dichloride,
thionyl chloride, sulfuryl chloride, thionyl bromide, and the
10 like;
halogenated titanium compounds such as titanium
tetrafluoride, titanium tetrachloride, titanium tetrabromide,
titanium tetraiodide, methoxytrichlorotitanium,
ethoxytrichlorotitanium, butoxytrichlorotitanium,
15 ethoxytribromotitanium, butoxytribromotitanium,
dimethoxydichlorotitanium, diethoxydichlorotitanium,
dibutoxydichlorotitanium, diethoxydibromotitanium,
trimethoxychlorotitanium, triethoxychlorotitanium,
tributoxychlorotitanium, triethoxybromotitanium and the like;
halogenatedsilane compounds suchas silicontetrachloride,
silicon tetrabromide, silicon tetraiodide,
methoxytrichlorosilane, ethoxytrichlorosilane,
butoxytrichlorosilane, ethoxytribromosilane,
butoxytribromosilane, dimethoxydichlorodsilane,
diethoxydichlorosilane,
diethoxydibromosilane,
triethoxychlorosilane,
triethoxybromosilane,
5 ethyltrichlorosilane,
phenyltrichlorosilane,
diethyldichlorosilane,
diphenyldichlorosilane,
triethylchlorosilane,
10 triphenylchlorosilane, and the like;
halogenated germanium compounds such as germanium
tetrafluoride, germanium tetrachloride, germanium tetraiodide,
methoxytrichlorogermanium, ethoxytrichlorogermanium,
butoxytrichlorogermanium, ethoxytribromogermanium,
15 butoxytribromogermanium, dimethoxydichlorogermanium,
diethoxydichlorogermanium, dibutoxydichlorogermanium,
diethoxydibromogermanium, trimethoxychlorogermanium,
triethoxychlorogermanium, tributoxychlorogermanium,
triethoxybromogermanium, and the like; and
halogenated tin compounds such as tin tetrafluoride, tin
tetrachloride, tin tetrabromide, tin tetraiodide,
methoxytrichlorotin, ethoxytrichlorotin, butoxytrichlorotin,
ethoxytribromotin, butoxytribromotin, dimethoxydichlorotin,
diethoxydichlorotin, dibutoxydichlorotin, diethoxydibromotin,
dibutoxydichlorosilane,
trimethoxychlorosilane,
tributoxychlorosilane,
methyltrichlorosilane,
butyltrichlorosilane,
dimethyldichlorosilane,
dibutyldichlorosilane,
trimethylchlorosilane,
tributylchlorosilane,
trimethoxychorotin, triethoxychlorotin, tributoxychlorotin,
triethoxybromotin, methyltrichlorotin, ethyltrichlorotin,
butyltrichlorotin, phenyltrichlorotin, dimethyldichlorotin,
diethyldichlorotin, dibutyldichlorotin, diphenyldichlorotin,
5 trimethylchlorotin, triethylchlorotin, tributylchlorotin,
triphenylchlorotin, and the like.
[0116]
These compounds may be used alone or in combination of two
or more kinds. Moreover, dilution is permissible using a
10 hydrocarbon or halogenated hydrocarbon.
[0117]
Of these compounds exemplified as the (C) component,
preferred examples include trialkylaluminums, alkenylaluminums,
dialkylaluminum halides, alkylaluminum sesquihalides,
15 alkylaluminum dihalides, alkylaluminum hydrides, alkylaluminum
alkoxides, (iso-Bu)2 Al (OSiMe3), (iso-Bu)2 Al (OSiEt3), Et2AlOAlEt2,
(iso-Bu)* AlOAl (iso-Bu)2 , LiAl (C2H5)4 r halogenated silane
compounds, and halogenated titanium compounds. Further
preferred examples are trialkylalurninums, alkenylaluminums,
20 dialkylaluminum halides, alkylaluminum sesquihalides,
alkylaluminum dihalides, alkylaluminum hydrides, and
alkylaluminum alkoxides. Still further preferred examples are
trialkylaluminums and alkylaluminum halides. Still further
preferred examples are triethylaluminum, triisobutylaluminum,
trihexylaluminum, trioctylaluminum, diethylaluminum
monochloride, diisobutylaluminum monochloride, ethylaluminum
sesquichloride, and ethylaluminum dichloride.
[(D) Organoaluminumoxy compound]
5 The (D) organoaluminumoxy compound capable of use as a
component of the olefin polymerization catalyst in the present
inventionmaybethe same organoaluminumoxycompounds usedinstep
2 for production of the aforementioned (A) fine particles.

10 The method of production of ethylene-based polymer
particles according to the present invention conducts, in the
presence of the olefin polymerization catalyst including the (A)
fine particles and the (B) transition metal compound as described
above, homopolymerization of ethylene or copolymerization of
15 ethylene and a linear or branched a-olefin having 3 to 20 carbon
atoms.
[0118]
In the method of production of ethylene-based polymer
particles of the present invention, polymerization may be
20 performed by either a gas phase polymerization method or liquid
phase polymerization method, such as suspension polymerization
and the like. Specific examples ofthe inert hydrocarbon solvent
capable of use in the liquid phase polymerization method include
aliphatic hydrocarbons such as propane, butane, pentane, hexane,
heptane, octane, decane, dodecane, kerosene, and the like;
alicyclic hydrocarbons such as cyclopentane, cyclohexane,
methylcyclopentane, and the like; aromatic hydrocarbons such as
benzene, toluene, xylene, and the like; halogenated hydrocarbons
5 such as ethylene chloride, chlorobenzene, dichloromethane, and
the like; and mixtures of such hydrocarbons. Olefin can also be
used as the solvent.
[0119]
In the olefin polymerization using the aforementionedtype
10 of olefin polymerization catalyst, the utilized amount of the (B)
component relative to 1 L reaction volume is normally lo-'' to 10
mrnol, and preferably is loe9 to 1 mmol in terms of metal element
within the (B) component. The amount of the (B) component per
1 g of the (A) component is normally to 100 mmol, and preferably
15 is to 50 mmol.
[0120]
Moreover, when the (C) component is used, the mole ratio
[ (C) /MI of the (C) component to the total transition metal atom
(M) in the (C) component and (B) component is normally 0.01 to
20 100,000, and preferably is 0.05 to 50,000.
[0121]
Moreover, when the (D) component is used, the mole ratio
[(D) /MI of the (D) component to the total transition metal atom
(M) in the (D) component and (B) component is normally 0.01 to
100,000, and preferably is 0.05 to 50,000.
[0122]
Lower limit ofthe polymerization temperature ofthe olefin
using this type of olefin polymerization catalyst is -2Ooc,
5 preferably is O°C, further preferably is 20°c, and particularly
furtherpreferablyis 30"~. Theupper limit ofthepolymerization
temperature of the olefin is 1 5 0 " ~pr~ef erably is 1 2 0 " ~fu~rt her
preferably is 100°C, and particularly preferably is 80"~.
[0123]
10 Particularly when the ethylene-based polymer particles
obtained by the present invention are used for solid-phase
stretch-molding, the aforementioned range of polymerization
temperature is thought to be particularly preferred from the
standpointofabalancebetweencatalyticactivityandsuppression
15 of entanglement of the polymer chains.
[0124]
Pressureofpolymerizationisnormallyatmosphericpressure
to 10 MPa, and preferably is atmospheric pressure to 5 MPa.
[0125]
20 The production method of the ethylene-based polymer of the
present invention may use a reaction divided into two or more
stages havingdifferentpolymerization reaction conditions, i.e.
the so-called multi-stage polymerization method.
[0126]
When t h e multi-stage polymerization method is adopted,
i n t r i n s i c v i s c o s i t y [q] of t h e ethylene-based polymer obtained
i n a c e r t a i n s i n g l e stage of t h e multi-stage polymerization
process is g r e a t e r than o r equal t o 2 dL/g and less than o r equal
5 t o 30 dL/g, p r e f e r a b l y is g r e a t e r than or equal t o 3 d ~ / gan d less
than or equal t o 28 dL/g, and f u r t h e r p r e f e r a b l y is g r e a t e r than
or equal t o 5 dL/g and less than or equal t o 25 dL/g.
[0127]
More s p e c i f i c a l l y , a p r e f e r r e d embodiment of t h e method of
10 production o f t h e ethylene-basedpolymer o f t h e present invention
includes the below described s t e p ( a ) and s t e p (b) a s an example
of the so-called two-stage polymerization. More i n d e t a i l ,
ethylene-based polymer produced i n the s t e p ( a ) p r e f e r a b l y has
an i n t r i n s i c v i s c o s i t y [q] g r e a t e r than or equal t o 2 dL/g and
15 less than or equal t o 30 dL/g, p r e f e r a b l y g r e a t e r than or equal
t o 3 d L / g a n d l e s s t h a n or equal t o 28 dL/g, and f u r t h e r p r e f e r a b l y
g r e a t e r than or equal t o 5 dL/g and less than or equal t o 25 dL/g.
In the other s t e p (abbreviated h e r e i n a f t e r as t h e s t e p (b) ) , the
ethylene-based polymer is p r e f e r a b l y produced under conditions
20 such t h a t t h e i n t r i n s i c v i s c o s i t y [q] exceeds 15 dL/g and is less
than or equal t o 50 dL/g, p r e f e r a b l y exceeds 20 dL/g and is less
than or equal t o 48 dL/g, and f u r t h e r p r e f e r a b l y exceeds 23 dL/g
and is less than or equal t o 45 dL/g. The s t e p ( a ) and s t e p (b)
preferably produce polymers having d i f f e r e n t [q] values.
SF-2399
l
[0128]
Although no particular limitation is placed on the order
of performance of the step (a) and step (b), when the step (a)
is the step for producing the relatively low molecular weight
5 ethylene-based polymer component, this step (a) is preferably
performed first, and the step (b) for producing the relatively
high molecular weight ethylene-based polymer component is
preferably performed thereafter. In this case, the intrinsic
viscosity of the component produced in step (a) may be obtained
10 as a measured value by sampling part of the component. Intrinsic
viscosity of the component produced in the step (b) is calculated
based on the below listed formula.
[0129]
Moreover, although the upper and lower limits of the mass
15 ratio of the component (a) formed in the step (a) and the component
(b) formed in step (b) are determined by the intrinsic viscosities
of the respective components, the upper limit of the component
(a) ispreferably50%, furtherpreferablyis 40%, andparticularly
further preferably is 35%. The lower limit is preferably 5%, and
20 further preferably is 10%. On the other hand, the upper limit
of the component (b) is preferably 95%, and more preferably 90%,
and the lower limit is so%, preferably 6O%, and more preferably
65%.
[0130]
This mass ratio can be determined by a method in which an
ethylene absorption is measured in each step, or a method in which
the resins in the respective steps are sampled in a small
prescribed amount, and the resin production amount in each step
5 is calculated from the mass, the slurry concentration, and the
content of catalyst components in the resin, and the like.
Further, the intrinsic viscosity of the polymer produced in the
second stage is calculated based on the following formula.
[0131]
10 [ql (1) xw(l)+[qI (2) xw(2)=[rlI (t)
(in the formula, [q] (1) is the intrinsic viscosity of the
polymer produced in step (a), [q](2) is intrinsic viscosity of
the polymer produced in step (b) , [q] (t) is the intrinsic viscosity
of the final product, w (1) is the mass fraction in the step (a),
15 and w(2) is the mass fraction in step (b))
The following is inferred as the reason why the
ethylene-based polymer of the present invention is preferably
produced by two-stage polymerization as describe above.
[0132]
20 When the polymerization reaction using the olefin
polymerization catalyst of the present invention is carried out
to polymerize ethylene (and another utilized olefin, as may be
required), the polymerization reaction occurs at catalyst active
sites within the catalyst component. Because the generated
SF-2399 * 67
polymer leaves the active site, the polymer generated at the
initial stage of the polymerization reaction is assumed to be
disproportionally located at the surface part of the generated
ethylene-basedpolymerparticle, and the polymer generatedatthe
5 later stage of the polymerization reaction is assumed to be
disproportionally located at the inner part of the composition
particle. That is to say, the generated ethylene-based polymer
particles are thought to have a structure resembling tree rings.
[0133]
10 Therefore, when the ethylene-based polymer is produced by
the present invention using two or more stages having separate
reaction conditions, and when the ethylene-based polymer is
produced under conditions such that intrinsic viscosity [q] of
the ethylene-based polymer produced in the first stage becomes
15 lower than intrinsic viscosity [I]] of the finally produced
ethylene-based polymer, it is thought that there is a high
possibility of the presence of relatively low molecular weight
polymer at the composite particle surface, and pressure bonding
is thought to thus occur easily between particles during
20 solid-phase stretch-molding. Since the ethylene-based polymer
isobtainedusinga specific catalyst as describedaboveaccording
to the present invention, the ethylene-based polymer is assumed
to be prepared so as to readily partially melt.
LO1341
SF-2399
68
Moreover, the olefin polymerization catalyst used in the
present invention is a so-calledsingle site catalyst. Thus, the
parts of the structure where the high molecular weight part and
low molecular weight parts are disproportionally present are
5 anticipatedtobe ratheruniformlyand finelydistributed. Thus,
during the below described solid-phase stretch-molding,
stretching occurs uniformly, andbreakage during stretching does
not occur easily. It is thus thought that a high stretch ratio
is exerted.
10 [0135]
The polymerization reaction of the ethylene-based polymer
of the present invention may be performed by the batch method,
semi-continuous method, or continuous method. The batch method
is preferablyadoptedwhenthe ethylene-basedpolymeris produced
15 by a multi-stage polymerization process in the aforementioned
manner. The ethylene-based polymer obtained by the batch method
is thought to be advantageous due to low particle-to-particle
variance in the ethylene-based polymers obtained in the first
stage polymerization step and in the second stage polymerization
20 step so that there is a uniformly dispersed structure.
[0136]
Molecular weight of the obtained olefin polymer may be
adjusted using hydrogen in the polymerization system or may be
adjusted by changing the polymerization temperature or
polymerization pressure. Furthermore, molecular weight of the
obtained olefin polymer may be adjusted by changing the amount
of the (C) component or (D) component present in the olefin
polymerization catalyst.
5 [0137]
Examples oftheolefinspolymerizedinthepresentinvention
are linear or branched a-olefins having 2 to 30 carbon atoms, and
preferably 2 to 20 carbon atoms, and at least including ethylene,
as exemplified by ethylene, propylene, 1-butene, 2-butene,
10 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene,
1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; and
cycloolefins having 3 to 30 carbon atoms, and preferably 3 to 20
carbon atoms, as exemplified by cyclopentene, cycloheptene,
15 norbornene, 5-methyl-2-norbornene, tetracyclododecene, and
2-methy1-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphtha
lene; polarmonomers s u c h a s a - a n d p - u n s a t u r a t e d c a r b o x y l i c a c i d s
as exemplified by acrylic acid, methacrylic acid, fumaric acid,
maleic anhydride, itaconic acid, itaconic anhydride, and
20 bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic acid; metallic salts
ofthesea-andp-unsaturatedcarboxylicacids suchas sodiumsalts,
potassium salts, lithium salts, zinc salts, magnesium salts,
calcium salts, and the like; a- and P-unsaturated carboxylic
esters suchasmethylacrylate, ethylacrylate, n-propylacrylate,
isopropyl acrylate, n-butyl acrylate, isobutyl acrylate,
tert-butylacrylate, 2-ethylhexylacrylate, methylmethacrylate,
ethyl methacrylate, n-propyl methacrylate, isopropyl
methacrylate, n-butyl methacrylate, isobutyl methacrylate, and
5 the like; vinyl esters such as vinyl acetate, vinyl propionate,
vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate,
vinyl trifluoroacetate, and the like; and unsaturated glycidyl
esters such as glycidyl acrylate, glycidyl methacrylate,
monoglycidyl itaconate, and the like. Furthermore,
10 vinylcyclohexane, dienes, polyenes, or the like are also
employable. The dienes and the polyenes are cyclic or linear
compoundshaving4to30 carbonatoms, andpreferably4to20 carbon
atoms, and having two or more double bonds. Specific examples
of such compounds include butadiene, isoprene,
ethylidene norbornene, vinyl norbornene, and dicyclopentadiene;
20 and 5,9-dimethyl-1,4,8-decatriene; as well as aromatic vinyl
compounds such as mono- or poly-alkylstyrenes (e.g., styrene,
I
I o-methylstyrene, m-methylstyrene, p-methylstyrene,
o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene,
p-ethylstyrene, or the like), functional group-containing
styrene derivatives (e.g., methoxystyrene, ethoxystyrere,
vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate,
hydroxystyrene, o-chlorostyrene, p-chlorostyrene,
divinylbenzene, or the like); and 3-phenylpropyrene,
5 4-phenylpropyrene, a-methylstyrene, or the like.

The ethylene-basedpolymerparticles obtainedbythemethod
of production of ethylene-based polymer particles according to
the present invention preferably have the below listed
10 characteristics.
[0138]
(i) Intrinsic viscosity [q] is in the range of 5 to 50 dL/g.
(ii) Average particle diameter is greater than or equal to
10 nm and less than 3,000 nm.
15 (iii) Crystallinity is at least 70%.
[0139]
The above intrinsic viscosity [q] is a value measured in
decalin at 135'C. The range of intrinsic viscosity [q] is 5 to
50 dL/g, preferably is 10 to 45 dL/g, and further preferably is
20 15 to 40 dL/g. Stretched fiber strength is insufficient when the
intrinsic viscosity is less than 5 dL/g. When the intrinsic
viscosity exceeds 50 dL/g, bonding of the grain boundaries of the
olefin powder is insufficient during press or stretching, and
uniform stretching becomes difficult.
[0140]
The aforementioned ethylene-based polymer particles are
formed as agglomerations of fine particles, and average particle
diameter ofthe fine particles is determined by observation using
a scanning electron microscope (SEM).
[0141]
Average particle diameter of the fine particles of the
ethylene-based polymer particles is greater than or equal to 10
nm and less than 3,000 nm, preferably greater than or equal to
10 nm and less than 2,000 nm, and further preferably greater than
or equal to 10 nm and less than 1,000 nrn. When ethylene-based
polymer particles havinga structure in the above range of average
particle diameter are contacted each other, contact area becomes
wide due to the high specific surface area, and pressure bonding
readilyoccursbetweenparticlesduringmoldingbythesolid-phase
stretch-molding method. As a result, breakage at the interfaces
between particles during stretching is hard to be generated, and
it becomes possible to mold at a high stretch ratio.
[0142]
Because the aforementionedethylene-basedpolymerparticle
is formed from an agglomeration of fine particles and wide spaces
are present between fine particles, the ethylene-based polymer
particles undergo uniform pressure bonding history during
pressure bonding and molding, and thus uniform structure having
* 73
few d e f e c t s can be formed. As a r e s u l t , breakage due t o d e f e c t s
during s t r e t c h i n g i s h a r d t o b e generated, a n d i t becomes p o s s i b l e
t o mold a t a high s t r e t c h r a t i o .
[0143]
5 The c r y s t a l l i n i t y of t h e ethylene-based polymer p a r t i c l e s
is the value c a l c u l a t e d b a s e d o n t h e heat of f u s i o n o b s e r v e d u s i n g
a d i f f e r e n t i a l scanning c a l o r i m e t e r (DSC). The lower l i m i t of
the c r y s t a l l i n i t y of the ethylene-based polymer p a r t i c l e s is
normally 70%, p r e f e r a b l y is 75%, and f u r t h e r p r e f e r a b l y is 80%.
10 As the c r y s t a l l i n i t y i n c r e a s e s , a molded a r t i c l e w i t h h i g h e r
strengthmaybe o b t a i n e d , anddeformationandwarping, i . e . volume
c o n t r a c t i o n or t h e l i k e , a r e less l i k e l y t o occur. Thus although
it ismeaningless t o s e t a corresponding value f o r t h e upper l i m i t
o f t h e c r y s t a l l i n i t y , i f t h e upper l i m i t o f t h e c r y s t a l l i n i t y w e r e
15 t o be set, the upper l i m i t of t h e c r y s t a l l i n i t y would be 99%,
p r e f e r a b l y 97%, and f u r t h e r p r e f e r a b l y 95%.
[0144]
The ethylene-based polymer p a r t i c l e s of t h e present
invention may b e obtained by polymerization or copolymerization
20 of the c i t e d o l e f i n s i n t h e presence of t h e aforementioned o l e f i n
polymerization c a t a l y s t .
[0145]
Of t h e s e , examples of t h e ethylene-basedpolymer p a r t i c l e s
crystalline copolymer mainly comprising ethylene and obtained by
copolymerizing ethylene and a small amount of a-olefins such as
propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-hexene,
1-octene and 1-decene. In view of increasing the crystallinity
and in view of stretchability in later-mentioned solid-phase
stretch-molding, the ethylene homopolymer is preferable.
However, if creep resistance is required in the molded product,
copolymer with propylene or the like is preferred. Depending on
the utilized olefin polymerization catalyst, ethylene-based
polymers having branched structures may be obtained even from
ethylene homopolymers. However, due to use of a supported type
olefin polymerization catalyst containing a specifiedtransition
metal compound, the ethylene-based polymer of the present
invention is thought to have extremelylittle such branching. If
a polymerization method capable of obtainingthis type of polymer
exists, the degree of freedom of control of molecular structure
becomes high, and this is advantageous for improving the
properties of below described solid-phase stretch-moldedarticle
or the like.

The stretch-moldedarticleobtainedfromtheethylene-based
polymer according tothe present invention is preparedbymolding
the ethylene-based polymer particle usingthe known polyethylene
stretch-molding method. The stretch-molded a r t i c l e of the
~ p r e s e n t invention is obtained from the ethylene-based polymer
p a r t i c l e s polymerized using the o l e f i n polymerization c a t a l y s t
comprising the f i n e p a r t i c l e s (i.e . , (A) component) obtained
5 through the s p e c i f i c steps as a n e s s e n t i a l c o n s t i t u e n t component.
Thus the stretch-molded a r t i c l e with l i t t l e entanglement of
polymer chains of the ethylene-based polymer can be obtained, and
it becomes possible t o mold a t a high s t r e t c h r a t i o . As a r e s u l t ,
d e g r e e o f o r i e n t a t i o n o f t h e o b t a i n e d m o l d e d a r t i c l e b e c o m e s h i g h ,
10 and high strength is r e a l i z e d . Because the ethylene-based
polymerparticle is formedfromanagglomerationof f i n e p a r t i c l e s
and wide spaces a r e present between f i n e p a r t i c l e s , the
ethylene-based polymer p a r t i c l e s undergo uniform pressure
bonding h i s t o r y during pressure bonding and molding, and thus
15 uniform s t r u c t u r e having few defects can be formed. Thus,
breakage due t o defects during s t r e t c h i n g i s h a r d t o b e generated,
and it becomes possible t o mold a t a high s t r e t c h r a t i o . As a
r e s u l t , degree of o r i e n t a t i o n of the obtained molded a r t i c l e
becomes high, and high strength is r e a l i z e d .
20 [0146]
The stretch-molded a r t i c l e of the present invention uses
ethylene-basedpolymerparticles havinghighintrinsicviscosity
[q] , and thus t h e r e is a tendency f o r the obtained molded a r t i c l e
t o have high s t r e n g t h . Furthermore, the stretch-molded a r t i c l e
* 7 6
of the present invention uses ethylene-based polymer particles
having a small average particle diameter. Thus specific surface
area is large, contact area between the ethylene-based polymer
particles becomes large during stretch-molding, and pressure
5 bonding readily occurs between particles. Thus, breakage at the
interfaces between particles during stretching is hard to be
generated, anditbecomespossibletomoldatahighstretchratio.
As a result, degree of orientation of the obtained molded article
becomes high, and high strength is realized.
10 [0147]
Among stretch-molded articles of the present invention,
particularly preferred stretch-molded articles are obtained by
the solid-phase stretch-molding method. Since the solid-phase
stretch-molding is a molding method without a solvent, molding
15 facility is relatively simple and adverse influence on
environments is small. Providing a stretch-molded article by
this type of method is thought to contribute highly to society.
[0148]
Extremely high stretchability is exerted when the
20 ethylene-based polymer particles of the present invention is
subjected to solid-phase stretch-molding. It is thus possible
to obtain articles having high strength, such as a fiber, film,
sheet, biomaterial such as bone replacement material, and the
like.
[ 0 1 4 9 ]
Any known conditions can be used without limitation for the
solid-phase stretch-molding except that the above-described
ethylene-based polymer must be used. For example, the
5 ethylene-basedpolymerofthepresentinventionispressurebonded
under a pressure of 1 MPa or more to mold a sheet, and the sheet
is then stretchedundertension at a relativelyhightemperature,
or stretched under pressure applied using a roll or the like.
Temperature of molding steps such as the pressure bonding step,
10 stretching step, and the like is preferably less than or equal
tothemeltingpointoftheparticlesoftheethylene-basedpolper
1 However, molding may be performed at a temperature greater than
1 or equal to the melting point as long as melt flow does not occur.
~ This temperature range preferably has an upper limit equal to the
15 melting point of the ethylene-based polymer of the present
invention plus 5°C and a lower limit equal to the melting point
minus 30°C.
[ 0 1 5 0 ]
Stretchability (i.e. stretch ratio) of the molded article
20 using the ethylene-based polymer of the present invention and
physical properties (i.e. stretch ratio, maximum stress during
stretching, andstrengthandelasticmodulusofthestretch-molded
article) of the obtained stretch-molded article are determined
as in the below described examples.
[0151]
When using the ethylene-based polymer particles of the
present invention, a stretch-molded article could be obtained at
a stretch ratio greater than or equal to 50, preferably greater
5 than or equal to 80, further preferably greater than or equal to
100, and particularly preferably greater than or equal to 120.
[0152]
By use of the ethylene-based polymer particles of the
present invention, tensile stress during stretching is low in
10 comparison to the conventional polymer. There is thus a tendency
to be able to stretch more uniformly. Stress during stretching
is preferably less than or equal to 30 MPa, further preferably
is less than or equal to 25 MPa, still further preferably is less
than or equal to 23 MPa, still further preferably is less than
15 or equal to 20 MPa, and particularly preferably is less than or
equal to 16 MPa.
[0153]
Due to the ability to mold at a high stretch ratio, the
stretch-molded article of the present invention is anticipated
20 to have high tensile elastic modulus and tensile strength.
Tensile elastic modulus of the obtained stretch-molded article
is preferably greater than or equal to 80 GPa, is further
preferably greater than or equal to 120 GPa, and is particularly
preferably greater than or equal to 140 GPa. Moreover, strength
7 9
o f t h e obtained stretch-molded a r t i c l e is p r e f e r a b l y g r e a t e r t h a n
or equal t o 2 GPa, is f u r t h e r p r e f e r a b l y g r e a t e r than or equal
t o 2.5 GPa, and is p a r t i c u l a r l y p r e f e r a b l y g r e a t e r than o r equal
t o 3 GPa.
EXAMPLES
[0154]
Next, t h e present invention w i l l be described based on
examples, but it is needless t o say t h a t t h e p r e s e n t invention
10 is not l i m i t e d t o t h e following examples unless d e v i a t i n g from
the g i s t .
[0155]
F o r t h e below described examples, average p a r t i c l e diameter
o f t h e f i n e p a r t i c l e s , the i n t r i n s i c v i s c o s i t y [ q ] , c r y s t a l l i n i t y ,
15 and average p a r t i c l e diameter of the ethylene-based polymer
p a r t i c l e s , and various types of physical p r o p e r t i e s of t h e
stretch-moldedarticleweremeasuredaccordingtothebelowlisted
methods.
(Average P a r t i c l e Diameter of Fine P a r t i c l e s )
20 A v e r a g e p a r t i c l e d i a m e t e r o f t h e fineparticleswasmeasured
by the dynamic l i g h t s c a t t e r i n g method using a Z e t a s i z e r Nano ZS
(manufactured by Sysmex Corporation) a t 25OC temperature i n
toluene s o l u t i o n .
( I n t r i n s i c Viscosity [q] )
Intrinsic viscosity [I]] was measured by dissolving the
ultrahigh molecular weight ethylene-based polymer particles in
decalin, and then performing measurement in decalin at 135'~
temperature.
5 (Crystallinity and Melting Point)
Crystallinity andmelting point were measured by the below
described method using DSC (model DSC 6220, manufactured by SII
Nano Technology Inc.) .
[0156]
10 Weight: about 5 mg
Heat-up rate: 10°C/minute
Measurement temperature range: 0°C to 200°C
Melting point: temperature at the top of the peak of fusion
Crystallinity: From70°~to1800~th,e amount of differential heat
15 is obtained by subtracting the baseline. Crystallinity is the
value obtained by dividing the obtained differential heat value
by290 J/g (i.e. heat of fusionof100% crystalline polyethylene).
(Scanning Electron Microscope (SEM))
Average particle diameter of the ethylene-based polymer
20 particles was measured at 10,000x magnification using a scanning
electronmicroscope (model JSM-6510LV, manufacturedby JEOLLtd.) .
10polymerparticleswere selectedfromwithintheobservedimage,
and average particle diameter was calculated for the selected
particles.
(Stretch Ratio)
The ethylene-based polymer particles were pressed at a
temperature of 136°C and a pressure of 7 MPa for 30 minutes to
manufacture a sheet with a thickness of about 500 pm, and the
5 obtained sheet was then cut into a rectangular shape that was 35
mm length and 7 mm breadth.
[0157]
A 10 rnrn diameter cylindrically shaped injection molded
product was produced using high density polyethylene, and this
10 molded product was halved along the center axis (hereinafter,
referred to as billet). The cut sheet was sandwiched and fixed
between the halved plane faces of the billet.
[0158]
A Capillary Rheometer IIB (manufactured by Toyo Seiki
15 Seisaku-sho, Ltd.) was heated to 120°C, and the previously
produced billet was set within the cylinder. The push rod was
u s e d t o p u s h o n t h e b i l l e t f r o m t h e t o p p a r t a t a r a t e o f 2 m m / s e c o n d
to perform compression stretching by causing the billet to pass
through a nozzle having a concave taper shape. Ratio of the
20 cross-sectional areas calculated based on the cylinder diameter
andthe discharge port diameter ofthe concave shapedtapernozzle
was 6 : 1. The sheet was stretched six-fold in the longitudinal
direction by passing through the nozzle.
[0159]
Thereafter, a sheet sample was cut from the stretched sheet
obtained in the pre-stretching, and the sheet sample was marked
by standard lines spaced 5 mm apart. The obtained sheet sample
was set (7mmchuckspacing) inatensiletester (Universal Testing
5 Instrument Model 1123, manufactured by Instron), and uniaxual
stretching was performed in the same direction as the
pre-stretching under 135"t~e mperature and 14 mm/minute tensile
speed conditions. The measurement was performed 3 to 5 times,
distance between the standard lines at break was divided by the
10 initial distance between the standard lines (5 mm), and the
resultant value was taken to be the second stretch ratio.
[0160]
The second stretch ratio was multiplied by 6, which was the
stretch ratio in the compression stretching, to give avaluewhich
15 was evaluated as the stretch ratio.
(Strength of the Stretch-molded Article)
Atensile tester (Universal Testing Instrument Model 1123,
manufactured by Instron) was used to measure tensile strength in
the stretch direction of the stretch-molded article cut into a
20 rectangular strip shape (23°C temperature, 30 mm chuck spacing,
30 mm/minute tensile speed conditions).
[Example 11
[Preparation of Component (a-l)]
76.2 g (0.80 mol) of anhydrous magnesium chloride, 332 g
83
ofdrydecane, 260.4 g (2.0mol) o f 2 - e t h y l h e x y l a l c o h o l , and119.4
g (0.4 mol) of 2-octyldodecyl alcohol were loaded i n t o a 2 L g l a s s
vessel equipped with an a g i t a t o r and s u f f i c i e n t l y purged with
nitrogen. Themixture was reacted f o r 4 hours a t 1 5 5 " ~ t o p r o d u c e
5 a uniform t r a n s p a r e n t s o l u t i o n . Thereafter, t h i s uniform
t r a n s p a r e n t s o l u t i o n was d i l u t e d using dry decane t o o b t a i n 0.2
mmol/mL (Mg atom b a s i s ) of uniform t r a n s p a r e n t component (a-1) .
[Preparation of Component ( A - l ) ]
1 L o f d r y t o l u e n e w a s l o a d e d i n t o a 2 L g l a s s v e s s e l e q u i p p e d
10 with an a g i t a t o r and s u f f i c i e n t l y purged with nitrogen. Liquid
temperature was maintained a t 50°c, and 4.0 mmol (Mg atom b a s i s )
of the component (a-1) was added. Thereafter, 16 mmol (A1 atom
b a s i s ) of triisobutylaluminum was slowly added dropwise t o
synthesize the f i n e p a r t i c l e component ( A - Part of t h i s
15 r e a c t i o n l i q u i d was sampled, and average p a r t i c l e diameter of t h e
f i n e p a r t i c l e measuredby t h e dynamic l i g h t s c a t t e r i n g m e t h o d was
40 nm.
[Ethylene Polymerization]
Ethylene was fed i n t o t h e r e a c t i o n l i q u i d containing t h e
20 component A - , and the l i q u i d phase and t h e gas phase were
s a t u r a t e d with e t h y l e n e . T h e r e a f t e r , l i q u i d temperature was
lowered t o 10°C, 0.002 mmol ( Z r atom b a s i s ) of t h e below l i s t e d
t r a n s i t i o n metal compound (B-1) was added, and polymerization
r e a c t i o n was performed f o r 30 minutes a t 1 0 ' ~ . After completion
of the polymerization, the reaction mixture was charged i n t o 4
L of methanol t o which hydrochloric acid had been added, and the
e n t i r e mass of polymer was made t o p r e c i p i t a t e . After recovery
by f i l t r a t i o n , the polymer was subjected t o preliminary drying
5 a t 8 0 ' ~un der vacuum f o r 1 hour. Then, the polymer was vacuum dried
f u r t h e r f o r 1 0 h o u r s a t l l O O c . 22.3 gofpolyethylenewas obtained.
C a t a l y t i c a c t i v i t y was 22.3 kg/mmol-Zr*h, and [q] was 18.7 dL/g.
Average p a r t i c l e diameter of the f i n e p a r t i c l e s composing the
polymer p a r t i c l e s was found t o be 190 nm (FIG. 1) by scanning
10 electron microscope observation. Polymer fouling was not
observed (FIG. 2) when t h e c o n d i t i o n o f t h e polymerization reactor
was checked.
[0161]
By using the obtained polyethylene a press sheet was
15 producedinthemannerdescribedforthe stretchratiomeasurement
method, and s t r e t c h r a t i o and strength of stretch-molded a r t i c l e
were measured. The r e s u l t s a r e shown i n Table 1.
[0162]
Component (B-1)
[Example 21
[Preparation of Component (A-2)]
500mLofdrytoluenewasloadedintoa1Lautoclaveequipped
with an a g i t a t o r and s u f f i c i e n t l y purged with n i t r o g e n . Liquid
5 temperature was maintained a t 50°c, and 0.32 mmol (Mg atom b a s i s )
of the component (a-1) synthesized i n the same manner a s Example
1 was added. Thereafter, 1.28 mmol (A1 atom b a s i s ) of
triisobutylaluminum was slowly added dropwise t o synthesize the
f i n e p a r t i c l e component (A-2). Part of t h i s r e a c t i o n l i q u i d was
10 sampled, and average p a r t i c l e diameter of t h e f i n e p a r t i c l e
measured by the dynamic l i g h t s c a t t e r i n g method was 40 nm.
[Ethylene Polymerization]
Ethylene was fed i n t o t h e r e a c t i o n l i q u i d containing t h e
component (A-2), and the l i q u i d phase and the gas phase were
15 s a t u r a t e d w i t h e t h y l e n e . Thereafter, 0.0004mmol ( Z r atombasis)
of the t r a n s i t i o n metal compound (B-1) was added, and
polymerizationreactionwasperformedfor30minutes a t 5 0 ° c w h i l e
feeding ethylene so a s t o r e a c h a t o t a l p r e s s u r e of 0.8 MPa. After
completion o f t h e polymerization, the obtainedpolymer was washed
20 using hexane. Then the polymer was subjected t o preliminary
d r y i n g a t 8 0 ° ~ u n d e r v a c u u m f o r 1 h o u r . Thenthepolymerwasvacuum
dried f u r t h e r f o r 10 hours a t llOOc. 62.8 g of polyethylene was
obtained. C a t a l y t i c a c t i v i t y w a s 314.0 kg/mmol-Zrmh, and [q] was
26.7 d ~ / g . Average p a r t i c l e diameter o f the f i n e p a r t i c l e s
composing the polymer p a r t i c l e s was found t o be 390 nm (FIG. 3)
byscanningelectronmicroscopeobservation. Polymer foulingwas
not observed (FIG. 4 ) when the condition of the polymerization
reactor was checked.
5 [0164]
The obtained polyethylene was used t o produce a press sheet
by the samemethod as d e s c r i b e d i n Example 1, and the s t r e t c h r a t i o
and strength of the stretch-molded a r t i c l e were measured. The
r e s u l t s a r e shown i n Table 1.
10 [Example 31
[Preparation of Component (A-3)]
500mLofdrytoluenewasloadedintoa1Lautoclaveequipped
with an a g i t a t o r and s u f f i c i e n t l y purged with nitrogen. Liquid
temperature was maintained a t 50 O C , and 0.16 rnmol (Mg atom b a s i s )
15 of the component (a-1) synthesized i n the same manner as Example
1 was added. Thereafter, 0.64 mmol (A1 atom b a s i s ) of
triisobutylaluminum was slowly added dropwise t o synthesize the
f i n e p a r t i c l e component (A-3). Part of t h i s reaction l i q u i d was
sampled, and average p a r t i c l e diameter of the f i n e p a r t i c l e
20 measured by the dynamic l i g h t s c a t t e r i n g method was 40 nm.
[Ethylene Polymerization]
Ethylene was fed i n t o the reaction l i q u i d containing the
component (A-3), and t h e l i q u i d phase and the gas phase were
s a t u r a t e d w i t h e t h y l e n e . T h e r e a f t e r , 0.0002 mmol ( Z r atombasis)
of below l i s t e d t r a n s i t i o n metal compound (B-2) was added, and
polymerizationreactionwasperformedfor 30minutes a t 5 0 ° c w h i l e
f e e d i n g e t h y l e n e soastoreachatotalpressureof 0.3MPa. After
completion o f t h e polymerization, t h e obtainedpolymer was washed
5 using hexane. Then the polymer was subjected t o preliminary
d r y i n g a t 8 0 ° ~ u n d e r v a c u u m f o r 1 h o u r . Thenthepolymerwasvacuum
d r i e d f u r t h e r f o r 10 hours a t l l O O ~ . 34.8 g of polyethylene was
obtained. C a t a l y t i c a c t i v i t y w a s 348.4 kg/mmol-Zr-h, and [I)] was
34.8 dL/g. Average p a r t i c l e diameter of t h e f i n e p a r t i c l e s
10 composing t h e polymer p a r t i c l e s was found t o be 300 nm (FIG. 5)
byscanningelectronmicroscopeobservation. Polymerfoulingwas
not observed (FIG. 6) when t h e condition of t h e polymerization
r e a c t o r was checked.
[0165]
The obtained polyethylene was used t o produce a press sheet
by the samemethod as d e s c r i b e d i n Example 1, and t h e s t r e t c h r a t i o
and s t r e n g t h of the stretch-molded a r t i c l e were measured. The
r e s u l t s a r e shown i n Table 1.
[0166]
Component (B-2)
[0167]
[Example 41
Ethylene was fed into the reaction liquid containing the
component (A-3) prepared in Example 3, and the liquid phase and
5 the gas phase were saturated with ethylene. Thereafter, 0.0002
mmol (Zr atom basis) of the transition metal compound (B-2) was
added, and polymerization reaction was performed for 30 minutes
at 6 5 "w~h ile feeding ethylene so as to reach a total pressure
of 0.3 MPa. After completion ofthe polymerization, the obtained
10 polymer was washed using hexane. Then the polymer was subjected
to preliminary drying at 8 0 "u~n der vacuum for 1 hour. Then the
polymer was vacuum dried further for 10 hours at 110"~. 30.4 g
of polyethylene was obtained. Catalytic activity was 304.0
kg/rnrnol-Zrah, and [q] was 28.4 dL/g. Average particle diameter
15 of the fine particles composing the polymer particles was found
tobe 310nm ( F I G . 7) byscanningelectronmicroscope observation.
Polymer fouling was not observed ( F I G . 8) when the condition of
the polymerization reactor was checked.
The obtained polyethylene was used to produce a press sheet
by the samemethodas describedinExample 1, andthe stretch ratio
and strength of the stretch-molded article were measured. The
results are shown in Table 1.
[Example 51
89
[Preparation of Component (a-2) 1
47.6 g (0.50 mol) of anhydrous magnesium c h l o r i d e , 65 g of
dry decane, 97.6 g (0.75 mol) of 2-ethylhexyl alcohol, and 223.9
g (0.75mol) o f 2 - o c t y l d o d e c y l a l c o h o l w e r e l o a d e d i n t o a 1 L g l a s s
5 vessel equipped with a n a g i t a t o r and s u f f i c i e n t l y purged with
nitrogen. Themixture was reacted f o r 4 hours a t 1 5 5 ° ~ t o p r o d u c e
a uniform t r a n s p a r e n t s o l u t i o n . Thereafter, t h i s uniform
t r a n s p a r e n t s o l u t i o n was d i l u t e d using dry decane t o o b t a i n 0.2
mmol/mL (Mg atom b a s i s ) of uniform t r a n s p a r e n t component ( a - 2 ) .
10 [Preparation of Component ( A - 4 ) ]
500mLofdrytoluenewasloadedintoa1Lautoclaveequipped
with an a g i t a t o r and s u f f i c i e n t l y purged with n i t r o g e n . Liquid
temperature was maintained a t 50°c, and 0.75 mmol (Mg atom b a s i s )
of the component (a-2) was added. Thereafter, 2.25 mmol (A1 atom
15 b a s i s ) of triisobutylaluminum was slowly added dropwise t o
synthesize t h e f i n e p a r t i c l e component ( A - 4 ) . Part of t h i s
r e a c t i o n l i q u i d w a s sampled, andaverage p a r t i c l e diameter o f t h e
f i n e p a r t i c l e measuredby the dynamic l i g h t scatteringmethodwas
30 nm.
20 [Ethylene Polymerization]
Ethylene was fed i n t o t h e r e a c t i o n l i q u i d containing the
component ( A - 4 ) , and t h e l i q u i d phase and t h e gas phase were
s a t u r a t e d w i t h e t h y l e n e . T h e r e a f t e r , 0.0015mmol ( T i atombasis)
of below l i s t e d t r a n s i t i o n metal compound (B-3) was added, and
polymerizationreactionwasperformedfor 30minutes a t 5 0 ° c w h i l e
feeding ethylene so as t o r e a c h a t o t a l p r e s s u r e o f 0.3MPa. After
completion o f t h e polymerization, the obtainedpolymer was washed
using hexane. Then the polymer was subjected t o preliminary
5 dryingat80°Cundervacuumfor1hour. Thenthepolymerwasvacuum
dried f u r t h e r f o r 10 hours a t llOOc. 28.5 g of polyethylene was
obtained. C a t a l y t i c a c t i v i t y was 38.0 kg/mmol-ti oh, and [q] was
23.8 dL/g. Average p a r t i c l e diameter of the f i n e p a r t i c l e s
composing the polymer p a r t i c l e s was found t o be 250 nm (FIG. 9)
10 byscanningelectronmicroscopeobservation. Polymer foulingwas
not observed (FIG. 10) when the condition of the polymerization
reactor was checked.
[0169]
The obtained polyethylene was used t o produce a press sheet
15 by the samemethodas describedinExample1, andthe s t r e t c h r a t i o
and strength of the stretch-molded a r t i c l e were measured. The
r e s u l t s are shown i n Table 1.
[0170]
Component (8-3)
e
[Example 61
[Preparation of Component (A-5)]
I 750 mL of dry toluene and 20.0 mmol (A1 atom basis) of
triisobutylaluminum were loaded into a 1 L glass vessel equipped
5 with an agitator and sufficiently purged with nitrogen. While
the mixture was strongly stirred using a homogenizer (model
CLEARMIX CLM-1.5S, manufactured by M Technique Co., Ltd.) at a
rotation rate of 15,000 rpm and while liquid temperature was
maintained at 20°c, 20 mmol (Mg atom basis) of component (a-1)
10 synthesized in the same manner as Example 1 was slowly added
dropwise, and the mixture was allowed to react for 15 minutes.
Thereafter, liquid temperature was raised to 50°c, and reaction
was performed for 3 minutes to synthesize the fine particle
component (A-5). Part of this reaction liquid was sampled, and
15 average particle diameter of the fine particle measured by the
dynamic light scattering method was 50 nm.
[Ethylene Polymerization]
500mLofdrytoluenewasloadedintoa1Lautoclaveequipped
with an agitator and sufficiently purged with nitrogen. Then
20 ethylene was fed, and the liquid phase and the gas phase were
saturated with ethylene. Thereafter, 0.05 mmol (A1 atom basis)
oftriisobutylaluminum, 0.50mrnol (Mg atombasis) ofthe component
(A-5), and 0.001 mmol (Ti atom basis) of the transition metal
compound (B-3) were added, and polymerization reaction was
92
performed f o r 30 minutes a t 50°c while feeding ethylene gas so
as t o reach a t o t a l pressure of 0.3 MPa. After completion of the
polymerization, the obtained polymer was washed using hexane.
Then the polymer was s u b j e c t e d t o p r e l i m i n a r y d r y i n g a t 80°cunder
5 vacuum f o r 1 hour. Then the polymer was vacuum dried f u r t h e r f o r
10 hours a t llOOc. 24.9 g of polyethylene was obtained.
C a t a l y t i c a c t i v i t y was 49.8 kg/mmol-Tiah, and [q] was 24.8 dL/g.
Average p a r t i c l e diameter of the f i n e p a r t i c l e s composing the
polymer p a r t i c l e s was found t o be 220 nm (FIG. 11) by scanning
10 electron microscope observation. Polymer fouling was not
observed (FIG. 12) when the condition of the polymerization
reactor was checked.
101721
The obtained polyethylene was used t o produce a press sheet
15 by the samemethodas describedinExample1, andthe s t r e t c h r a t i o
and strength of the stretch-molded a r t i c l e were measured. The
r e s u l t s a r e shown i n Table 1.
[Example 71
[Preparation of Component (A-6)J
20 500mLofdrytoluenewasloadedintoa1Lautoclaveequipped
with an a g i t a t o r and s u f f i c i e n t l y purged with nitrogen. Liquid
temperature was maintained a t 50°c, and 1 . 0 mmol (Mg atom b a s i s )
of the component (a-1) synthesized i n the same manner as Example
1 was added. Thereafter, 3.0 mmol (A1 atom b a s i s ) of
triisobutylaluminum was slowly added dropwise to synthesize the
fine particle component (A-6). Part of this reaction liquid was
sampled, and average particle diameter of the fine particle
measured by the dynamic light scattering method was 40 nm.
5 [Ethylene Polymerization]
Ethylene containing 500 ppm of hydrogen was fed into the
reaction liquid containing the component (A-6), and the liquid
phase and gas phase were saturated. Thereafter, 0.005 mmol (Ti
atom basis) of below listed transition metal compound (B-4) was
10 added, and polymerization reaction was performed for 30 minutes
at 50°C while feeding ethylene containing 500 ppm of hydrogen so
as to reach a total pressure of 0.8 MPa. After completion of the
polymerization, the obtained polymer was washed using hexane.
Then the polymer was s u b j e c t e d t o p r e l i m i n a r y d r y i n g at 80°cunder
I
I 15 vacuum for 1 hour. Then the polymer was vacuum dried further for
10 hours at 110"~. 43.3 g of polyethylene was obtained.
Catalytic activity was 17.3 kg/mmol-Tiah, and [q] was 23.8 dL/g.
Average particle diameter of the fine particles composing the
polymer particles was found to be 150 nm (FIG. 13) by scanning
20 electron microscope observation. Polymer fouling was not
observed (FIG. 14) when the condition of the polymerization I
reactor was checked.
[0173]
1 The obtained polyethylene was used to produce a press sheet
[Example 81
by t h e samemethodas describedinExample 1, a n d t h e s t r e t c h r a t i o
and s t r e n g t h of t h e stretch-molded a r t i c l e were measured. The
r e s u l t s a r e shown i n Table 1.
= Component (B-4)
with an a g i t a t o r and s u f f i c i e n t l y purged with n i t r o g e n . Then
10 ethylene c o n t a i n i n g 500 ppm of hydrogen was fed t o s a t u r a t e t h e
l i q u i d p h a s e and gas phase. T h e r e a f t e r , 0.04 mmol ( A l a t o m b a s i s )
oftriisobutylaluminum, 0.40mmol (Mg atombasis) o f t h e component
(A-5) produced i n Example 6, and 0.002 mmol ( T i atom b a s i s ) of
t h e t r a n s i t i o n m e t a l compound (B-4) wereadded, a n d w h i l e e t h y l e n e
15 containing 500 ppm of hydrogen was fed so a s t o maintain t o t a l
pressure a t 0.8 MPa, t h e polymerization r e a c t i o n was performed
f o r 30 minutes a t 5 0 ' ~ . A f t e r completion of t h e polymerization,
t h e obtained polymer was washed using hexane. Then t h e polymer
was subjected t o p r e l i m i n a r y d r y i n g a t 80°c under vacuum f o r 1
20 hour. Then t h e polymer was vacuum d r i e d f u r t h e r f o r 10 hours a t
110°C. 26.5 g of polyethylene was obtained. C a t a l y t i c a c t i v i t y
was 26.5 kg/mmol-Tiah, and [q] was 27.5 dL/g. Average p a r t i c l e
diameter of the f i n e p a r t i c l e s composing the polymer p a r t i c l e s
was found t o be 230 nm (FIG. 15) by scanning e l e c t r o n microscope
5 observation. Polymer fouling was not observed (FIG. 16) when the
condition of the polymerization reactor was checked.
[0176]
The obtainedpolyethylene was u s e d t o produce a press sheet
by the samemethodas describedinExample 1, andthe s t r e t c h r a t i o
10 and strength of the stretch-molded a r t i c l e were measured. The
r e s u l t s are shown i n Table 1.
[Example 91
[Preparation of Component (a-3)]
47.6 g (0.50 mol) of anhydrous magnesium chloride, 65 g of
15 dry decane, 97.6 g (0.75 mol) of 2-ethylhexyl alcohol, and 223.9
g (0.75mol) of 2-octyldodecylalcoholwereloadedinto a 1 L glass
vessel equipped with an a g i t a t o r and s u f f i c i e n t l y purged with
nitrogen. Themixture was reacted f o r 4 hours at155"Ctoproduce
a uniform transparent component (a-3).
20 [Preparation of Component (A-7)]
100 mL (100 mmol; Mg atom b a s i s ) of the component (a-3) and
89.6 g (300 mmol) of 2-octyldodecyl alcohol were loaded i n t o a
1 L g l a s s vesselequippedwithan a g i t a t o r and s u f f i c i e n t l y p u r g e d
withnitrogen, andthereactionwasperformedfor 4 hours a t 1 5 5 " ~ .
Thereafter, the reaction mixture was cooled down to O'C, and 50
mLofdrydecane, and560mLofdrychlorobenzenewereadded. While
the mixture was strongly stirred using a homogenizer (model
CLEARMIX CLM-1.5S, manufactured by M Technique Co., Ltd.) at a
5 rotation rate of 15,000 rpm, and while liquid temperature was
maintained at O'C, 138 mmol of triethylaluminum was slowly added
dropwise. Thereafter, the liquid temperature was raised to 80'~
over 4 hours, and while temperature was maintained at 80°c, 158
mmol of triethylaluminum was again slowly added dropwise. The
10 mixture was reacted further for 1 hour. After completion of the
reaction, the solidportionwas recoveredby filtrationandwashed
sufficiently using dry toluene, and dry toluene was added to
synthesize the fine particle component (A-7). Part of this
reaction liquidwas sampled, and average particle diameter ofthe
15 fine particlemeasuredby the dynamic light scattering methodwas
150 nm.
[Preparation of Solid Catalyst Component (E)]
100 mL of dry toluene was loaded into a 300 mL glass vessel
equipped with an agitator and sufficiently purged with nitrogen.
20 5.0 mrnol (Mg atom basis) of the fine particle component (A-7)
prepared as above were added. Thereafter, 0.025 mmol (Zr atom
basis) of a toluene solution of below listed transition metal
compound (B-5) was added dropwise, and the solid catalyst
component ( E ) was synthesized by reaction for 1 hour at room
temperature.
[Ethylene Polymerization]
with an agitator and sufficiently purged with nitrogen. Then
5 ethylene was fed, and the liquid phase and the gas phase were
saturated with ethylene. Thereafter, 1.25 mmol (A1 atom basis)
of triethylaluminum and 0.00015 mmol (Zr atom basis) of the solid
catalyst component (E) were added. While ethylene gas was fed
so as to maintain total pressure at 0.8 MPa, the polymerization
10 reaction was performed for 1 hour at 65OC. After completion of
the polymerization, the obtainedpolymerwas washedusinghexane.
Thenthe polymer was s u b j e c t e d t o p r e l i m i n a r y d r y i n g at 80°cunder
vacuum for 1 hour. Then the polymer was vacuum dried further for
10 hours at 110°C. 15.6 g of polyethylene was obtained.
15 Catalytic activity was 103.7 kg/mmol-Zrah, and [I]] was 20.0 dL/g.
Average particle diameter of the fine particles composing the
polymer particles was found to be 1050 nm (FIG. 17) by scanning
electron microscope observation. Polymer fouling was not
observed when the condition of the polymerization reactor was
20 checked.
[0177]
The obtained polyethylene was used to produce a press sheet
by the samemethod as describedin Example 1, and the stretch ratio
and strength of the stretch-molded article were measured. The
results are shown in Table 1.
Component (B-5)
[0179]
5 [Example 101
[Preparation of Component (a-4)]
95.2 g (1.0 mol) of anhydrous magnesium chloride, 442 mL
of dry decane, and 390.6 g (3.0 mol) of 2-ethylhexyl alcohol were
loaded into a 2 L glass vessel equipped with an agitator and
10 sufficiently purged with nitrogen. The mixture was reacted for
4 hours at 145'~ to produce a uniform transparent solution.
Thereafter, this uniform transparent solution was diluted using
dry decane to obtain a 0.2 rnmol/mL (Mg atom basis) solution.
Thereafter, 500 mL of dry toluene was loaded into a 1 L autoclave
15 equipped with an agitator and sufficiently purged with nitrogen.
Liquid temperature was maintained at 50°C, 0.80 mL of the
previously obtained solution was added, 0.96 mmol of isobutyl
alcoholwas slowlyalsoaddeddropwise, andthemixturewas stirred
for 15 minutes to obtain the component (a-4).
20 [Preparation of Component (A-8)]
1.68 mmol (A1 atom b a s i s ) of triethylaluminum was slowly
addeddropwisetotheentireamountofthecomponent (a-4) obtained
by the above preparation method and the f i n e p a r t i c l e component
(A-8) was synthesized. Part of t h i s reaction l i q u i d was sampled,
5 and average p a r t i c l e diameter of the f i n e p a r t i c l e measured by
the dynamic l i g h t s c a t t e r i n g method was 70 nm.
[Ethylene Polymerization]
Ethylene was fed i n t o the reaction l i q u i d containing the
component (A-8), and the l i q u i d phase and the gas phase were
10 s a t u r a t e d w i t h e t h y l e n e . T h e r e a f t e r , 0.0001rnmol ( Z r atombasis)
of the t r a n s i t i o n metal compound (B-2) was added, and
polymerizationreactionwasperformedfor30minutes a t 5 0 ° c w h i l e
feeding ethylene so as t o r e a c h a t o t a l p r e s s u r e o f 0.3MPa. After
completion o f t h e polymerization, the obtainedpolymerwas washed
15 using hexane. Then the polymer was subjected t o preliminary
d r y i n g a t 8 0 ° ~ u n d e r v a c u u m f o r 1 h o u r . Thenthepolymerwasvacuum
dried f u r t h e r f o r 10 hours a t llOOc. 14.8 g of polyethylene was
obtained. C a t a l y t i c a c t i v i t y w a s 296.2 kg/mmol-Zrmh, and [q] was
29.7 dL/g. Average p a r t i c l e diameter of the f i n e p a r t i c l e s
20 composing the polymer p a r t i c l e s was found t o be 690 nm (FIG. 18)
byscanningelectronmicroscopeobservation. Polymer foulingwas
not observed (FIG. 19) when the condition of the polymerization
reactor was checked.
[0180]
The o b t a i n e d p o l y e t h y l e n e was u s e d t o produce a p r e s s sheet
by the samemethodas describedinExample 1, a n d t h e s t r e t c h r a t i o
and s t r e n g t h of t h e stretch-molded a r t i c l e were measured. The
r e s u l t s a r e shown i n Table 1.
5 [Example 111
[Preparation of Component ( a - 5 ) ]
95.2 g (1.0 mol) of anhydrous magnesium c h l o r i d e , 442 mL
of dry decane, and 390.6 g (3.0 mol) of 2-ethylhexyl alcohol were
loaded i n t o a 2 L g l a s s v e s s e l equipped with an a g i t a t o r and
10 s u f f i c i e n t l y purged with nitrogen. The mixture was reacted f o r
4 hours a t 1 4 5 ' ~ t o produce a uniform t r a n s p a r e n t s o l u t i o n .
Thereafter, t h i s uniform t r a n s p a r e n t s o l u t i o n was d i l u t e d using
dry decane t o o b t a i n a 0.2 mmol/mL (Mg atom b a s i s ) s o l u t i o n .
Thereafter, 500 mL of dry heptane was loaded i n t o a 1 L autoclave
15 equipped with an a g i t a t o r and s u f f i c i e n t l y purged with nitrogen.
~ i q u i d t e m p e r a t u r e w a s m a i n t a i n e d a t 5 0 ~ C0 .,8 m L o f t h e p r e v i o u s l y
obtained s o l u t i o n was added, 0.96 mmol of i s o b u t y l alcohol was
slowly a l s o added dropwise, and t h e mixture was s t i r r e d f o r 15
minutes t o o b t a i n t h e component ( a - 5 ) .
20 [Preparation of Component (A-9)]
1.68 mmol (A1 atom b a s i s ) of triethylaluminum was slowly
addeddropwisetotheentireamountofthecomponent (a-5) obtained
by the above p r e p a r a t i o n method and t h e f i n e p a r t i c l e component
(A-9) was synthesized. Part of t h i s r e a c t i o n l i q u i d was sampled,
and average p a r t i c l e diameter of the f i n e p a r t i c l e measured by
the dynamic l i g h t s c a t t e r i n g method was 80 nm.
[Ethylene Polymerization]
Ethylene was fed i n t o the reaction l i q u i d containing the
5 component (A-9), and t h e l i q u i d phase and the gas phase were
s a t u r a t e d w i t h e t h y l e n e . Thereafter, 0.0001mmol ( Z r atombasis)
of the t r a n s i t i o n metal compound (B-2) was added, and
polyrnerizationreactionwasperformedfor 30minutes at50°Cwhile
feeding ethylene soastoreachatotalpressureof 0.3MPa. After
10 completion o f t h e polymerization, the obtainedpolymer was washed
using hexane. Then the polymer was subjected t o preliminary
d r y i n g a t 8 0 ° ~ u n d e r v a c u u m f o r 1 h o u r . Thenthepolymerwasvacuum
dried f u r t h e r f o r 10 hours a t l l O ° C . 22.6 g of polyethylene was
obtained. C a t a l y t i c a c t i v i t y w a s 452.0 kg/mmol-Zrmh, and [q] was
15 28.6 dL/g. Average p a r t i c l e diameter of the f i n e p a r t i c l e s
composing the polymer p a r t i c l e s was found t o be 840 nm (FIG. 20)
byscanningelectronmicroscopeobservation. Polymerfoulingwas
not observed (FIG. 21) when the condition of the polymerization
reactor was checked.
20 [0181]
The obtainedpolyethylene was u s e d t o produce a press sheet
bythe samemethodas describedinExample 1, andthe s t r e t c h r a t i o
and strength of the stretch-molded a r t i c l e were measured. The
r e s u l t s are shown i n Table 1.
*
[Example 121
[Preparation of Component (A-lo)]
with an agitator and sufficiently purged with nitrogen. Liquid
5 temperature was maintained at 50°c, and 0.24 mmol (Mg atom basis)
of the component (a-1) synthesized in the same manner as Example
1 was added. Thereafter, 0.96 mmol (A1 atom basis) of
triisobutylaluminum was slowly added dropwise to synthesize the
fine particle component (A-10). Part of this reaction liquid was
10 sampled, and average particle diameter of the fine particle
measured by the dynamic light scattering method was 40 nm.
[Ethylene Polymerization]
Ethylene was fed into the reaction liquid containing the
component (A-lo), and the liquid phase and the gas phase were
15 saturatedwithethylene. Thereafter, 0 . 0 0 0 3 m r n o l ( Z r a t o m b a s i s )
ofthe transitionmetal compound (B-2) wasloaded. While ethylene
gas containing 1,000 ppm of hydrogen was fed at an ethylene flow
rate of 0.5 L/minute, the polymerization reaction was performed
for 15 minutes at 50'~. After completion of the reaction, the
20 reactor was depressurized, and then while ethylene was fed to be
a total pressure of 0.3 MPa, the polymerization reaction was
performed for 25 minutes at 50'~. After completion of the
polymerization, the obtained polymer was washed using hexane.
Then the polymer was s u b j e c t e d t o p r e l i m i n a r y d r y i n g at 80°cunder
vacuum f o r 1 hour. Then t h e polymer was vacuum d r i e d f u r t h e r f o r
10 hours a t 110°C. 41.8 g of polyethylene was obtained.
C a t a l y t i c a c t i v i t y was 209.0 kg/mmol-Zrah. [q] of polyethylene
obtained i n s t e p ( a ) was 18.2 dL/g, and t o t a l [q] was 33.9 dL/g.
5 Average p a r t i c l e diameter of t h e f i n e p a r t i c l e s composing the
polymer p a r t i c l e s was found t o be 305 nm (FIG. 22) by scanning
e l e c t r o n microscope observation. Polymer f o u l i n g was not
observed (FIG. 23) when the condition of t h e polymerization
r e a c t o r was checked.
10 [0182]
The o b t a i n e d p o l y e t h y l e n e was u s e d t o produce a p r e s s sheet
by t h e samemethod as d e s c r i b e d i n Example 1, and t h e s t r e t c h r a t i o
and s t r e n g t h of t h e stretch-molded a r t i c l e were measured. The
r e s u l t s a r e shown i n Table 2.
15 [Example 131
[Ethylene Polymerization]
Ethylene was fed i n t o t h e r e a c t i o n l i q u i d containing the
component ( A - l o ) , and t h e l i q u i d phase and the gas phase were
s a t u r a t e d w i t h e t h y l e n e . Thereafter, 0.0003mrnol(Zratombasis)
20 o f t h e t r a n s i t i o n m e t a l compound (B-2) wasloaded. While ethylene
g a s containing 2,000 ppm of hydrogen was fed a t an ethylene flow
r a t e of 0.5 L/minute, t h e polymerization r e a c t i o n was performed
f o r 15 minutes a t 50°C. After completion of t h e r e a c t i o n , t h e
r e a c t o r was depressurized, and then while ethylene was fed t o be
a t o t a l pressure of 0.3 MPa, the polymerization reaction was
performed f o r 31 minutes a t 5 0 ' ~ . After completion of the
polymerization, the obtained polymer was washed using hexane.
Then the polymer was s u b j e c t e d t o p r e l i m i n a r y d r y i n g a t 80°cunder
5 vacuum f o r 1 hour. Then the polymer was vacuum dried f u r t h e r f o r
10 hours a t llO°C. 34.3 g of polyethylene was obtained.
C a t a l y t i c a c t i v i t y was 149.0 kg/mmol-Zroh. [q] of polyethylene
obtained i n s t e p ( a ) was 20.8 dL/g, and t o t a l [q] was 34.7 dL/g.
Average p a r t i c l e diameter of the f i n e p a r t i c l e s composing the
10 polymer p a r t i c l e s was found t o be 257 nm (FIG. 24) by scanning
electron microscope observation. Polymer fouling was not
observed (FIG. 25) when the condition of the polymerization
reactor was checked.
[0183]
15 The obtainedpolyethylene was usedtoproduce a p r e s s sheet
by the same method as d e s c r i b e d i n Example 1, and the s t r e t c h r a t i o
and strength of the stretch-molded a r t i c l e were measured. The
r e s u l t s a r e shown i n Table 2.
[Example 1 4 1
20 [Ethylene Polymerization]
Ethylene was fed i n t o the reaction l i q u i d containing the
component ( A - l o ) , and t h e l i q u i d phase and the gas phase were
s a t u r a t e d w i t h e t h y l e n e . T h e r e a f t e r , 0.0003mmol ( Z r atombasis)
o f t h e t r a n s i t i o n m e t a l compound (B-2) wasloaded. While ethylene
gas containing 1,000 ppm of hydrogen was fed at an ethylene flow
rate of 0.5 L/minute, the polymerization reaction was performed
for 7.5 minutes at 50°C. After completion of the reaction, the
reactor was depressurized, and then while ethylene was fed to be
5 a total pressure of 0.3 MPa, the polymerization reaction was
performed for 23 minutes at 50'~. After completion of the
polymerization, the obtained polymer was washed using hexane.
Then the polymer was s u b j e c t e d t o p r e l i m i n a r y d r y i n g at 80°cunder
vacuum for 1 hour. Then the polymer was vacuum dried further for
10 10 hours at 110°C. 42.7 g of polyethylene was obtained.
Catalytic activity was 280.2 kg/mmol-Zrmh. [q] of polyethylene
obtained in step (a) was 18.2 dL/g, and total [q] was 34.1 dL/g.
Average particle diameter of the fine particles composing the
polymer particles was found to be 286 nm (FIG. 26) by scanning
15 electron microscope observation. Polymer fouling was not
observed (FIG. 27) when the condition of the polymerization
reactor was checked.
[0184]
The obtained polyethylene was used to produce a press sheet
20 bythe samemethodas describedinExample1, andthe stretch ratio
and strength of the stretch-molded article were measured. The
results are shown in Table 2.
[Comparative Example 11
500 mL of dry toluene was loaded into a 1 L glass vessel
equipped with an agitator and sufficiently purged with nitrogen.
Then ethylene was fed, and the liquid phase and the gas phase were
saturated with ethylene. Liquid temperature was lowered to 5 " ~ ,
and 0.50 mmol (A1 atom basis) of methylaluminoxane (sometimes
5 referred to hereinafter as MAO) and 0.0008 mmol (Zr atom basis)
of the transition metal compound (B-1) were added, and the
polymerization reaction was performed for 30 minutes at 10°C.
After completion of the polymerization, the reaction mixture was
charged into 2 L of methanol to which hydrochloric acid had been
10 added, and the entire mass of polymer was made to precipitate.
After recovery by filtration, the polymer was subjected to
preliminary drying at 80°C under vacuum for 1 hour. Then, the
polymer was vacuum dried further for 10 hours at 110"~. 5.5 g
of polyethylene was obtained. Catalytic activity was 24.9
15 kg/mmol-Zrah, and [q] was 38.5 dL/g. When the obtained polymer
particles were observed using a scanning electron microscope,
agglomerates having fine-particle morphology were not observed
(FIG. 28).
[0185]
20 The obtained polyethylene was used to produce a press sheet by
the same method as described in Example 1, and the stretch ratio
and strength of the stretch-molded article were measured. The
results are shown in Table 3.
[0186]
The phenomenon of attachment of the polymer to the
polymerization reactor wall, i.e. so-calledfouling, occurred for
the present catalyst system (FIG. 29) . Moreover, stretchability
of the obtained polyethylene was low, and strength of the
5 stretch-molded article was low.
[Comparative Example 21
with an agitator and sufficiently purged with nitrogen. Then
ethylene gas was fed to saturate the liquid phase and gas phase.
10 Thereafter, 1.25 mmol (A1 atom basis) of methylaluminoxane and
0.001 mmol (Ti atom basis) of the transition metal compound (B-4)
were added, and the polymerization reaction was performed for 30
minutes at 50°c while feeding ethylene so as to reach a total
pressure of 0.3 MPa. After completion of the polymerization, the
15 reaction mixture was charged into 2 L of methanol to which
hydrochloric acid had been added, and the entire mass of polymer
was made to precipitate. After recovery by filtration, the
polymer was subjected to preliminary drying at 80°c under vacuum
forlhour. Then, the polymer was vacuumdriedfurther for10 hours
20 atllOOc. 9.9gofpolyethylenewasobtained. Catalyticactivity
was 19.5 kg/mmol-Timh, and [q] was 36.5 dL/g. When the obtained
polymer particles were observed using a scanning electron
microscope, agglomerates having fine-particle morphology were
not observed (FIG. 30) .
[0187]
The obtainedpolyethylenewas usedtoproduce a press sheet
by the samemethodas describedinExample 1, and the stretch ratio
and strength of the stretch-molded article were measured. The
results are shown in Table 3.
[0188]
Stretchability of the obtained polyethylene and strength
ofthe stretch-moldedarticlewerehigh. However, the phenomenon
of attachment of the polymer to the polymerization reactor wall,
i.e. so-called fouling, occurred forthe present catalyst system
(FIG. 31).
Comparative Example 3
[Preparation of Solid Component (W)]
Under flowing nitrogen, 30 g of silica gel (Si02) (5 pm
average particle diameter, dried for 5 hours at 150'~) was
suspended in 470 mL of dry toluene. Thereafter, in an ice bath,
130 mL of a toluene solution of methylaluminoxane (3.07 mrnol/mL,
A1 atom basis) was added dropwise over 30 minutes at OOc. After
completion of dropwise addition, the mixture was stirred for 30
minutes in the ice bath. Thereafter, the mixture was heated to
9 5 "a~n d was allowed to react for 4 hours. After completion of
the reaction, the supernatant liquid was removed by decantation,
and the obtained solid component was washed three times using dry
toluene to prepare a toluene slurry of the solid component (W) .
a
[0189]
A p a r t of the s o l i d component ( W ) obtained was c o l l e c t e d
t o examine the concentration. It was found t h a t the s l u r r y
concentrationwas 0.15 g/mL, andAlconcentrationwas 1.20mmol/mL,
5 Al/Si r a t i o was 0.81 (mole r a t i o ) . Average p a r t i c l e diameter by
Coulter counter was 5.3 pm.
[Preparation of Solid Catalyst Component ( X ) ]
150 mL of dry toluene was loaded i n t o a 300 mL glass vessel
equipped with an a g i t a t o r and s u f f i c i e n t l y purged with nitrogen.
10 Then 1.34 g ( s o l i d s b a s i s ) of the toluene s l u r r y of t h e s o l i d
component ( W ) prepared i n the above was added. Thereafter, 40.0
mL of a toluene solution of t h e t r a n s i t i o n metal compound (B-1)
(O.OOlmmol/rnL, Z r atombasis) was addeddropwise, and themixture
was reacted f o r 1 hour a t room temperature. After completion of
15 the reaction, the supernatant l i q u i d was removed by decantation,
and the obtained s o l i d component was washed t h r e e times using dry
toluene and two times using dry decane t o prepare a decane s l u r r y
of the s o l i d c a t a l y s t component (X) . A p a r t of the decane s l u r r y
of the s o l i d c a t a l y s t component (X) obtained was c o l l e c t e d t o
20 examine the concentration. It was found t h a t Z r concentration
was 0.000363 mmol/mL, and A1 concentration was 0.0919 mmol/mL.
[Ethylene Polymerization]
500mLofdryheptanewasloadedintoa1Lautoclaveequipped
with an a g i t a t o r and s u f f i c i e n t l y purged with nitrogen. Then
ethylene was fed, and t h e l i q u i d phase and the gas phase were
s a t u r a t e d with ethylene. Thereafter, 0.35 mmol (A1 atom b a s i s )
oftriisobutylaluminurnand 0.002 mmol ( Z r atombasis) o f t h e s o l i d
c a t a l y s t component (X) prepared i n the aforementionedmannerwere
5 added. After 25 mL of hydrogen was f u r t h e r added, the
polymerization reaction was performed f o r 1 hour a t 5 0 ' ~w hile
e t h y l e n e w a s f e d s o a s t o m a i n t a i n t o t a l p r e s s u r e a t 0 . 8 M P a . After
completion o f t h e polymerization, the obtainedpolymer was washed
using hexane. Then the polymer was subjected t o preliminary
i 10 d r y i n g a t 8 0 ' ~ u n d e r v a c u u m f o r 1 h o u r . Thenthepolymerwasvacuum
dried f u r t h e r f o r 10 hours a t llO°C. 63.1 g of polyethylene was
obtained. C a t a l y t i c a c t i v i t y was 31.6 kg/mmol-Zrah, and [q] was
19.2 dL/g. When the obtained polymer p a r t i c l e s were observed
using a scanning electron microscope, agglomerates having
15 f i n e - p a r t i c l e morphology were not observed (FIG. 32). Polymer
fouling was not observed (FIG. 33) when the condition of the
polymerization reactor was checked.
[0190]
The obtainedpolyethylene was u s e d t o produce a press sheet
20 by the samemethod as d e s c r i b e d i n Example 1, and the s t r e t c h r a t i o
and strength of the stretch-molded a r t i c l e were measured. The
r e s u l t s a r e shown i n Table 3. The obtained polyethylene had low
s t r e t c h a b i l i t y , and strength of the stretch-molded a r t i c l e was
low.
r)
[Comparative Example 41
[Preparation of Solid Component (Y)]
95.2 g (1.0 mol) of anhydrous magnesium chloride, 442 mL
of dry decane, and 390.6 g (3.0 mol) of 2-ethylhexyl alcohol were
5 loaded into a 2 L glass vessel equipped with an agitator and
sufficiently purged with nitrogen. The mixture was reacted for
4 hours at 145OC to produce a uniform transparent solution.
Thereafter, 100 mL (100 mmol, Mg atom basis) of the uniform
transparent solutionand 610mLof drydecanewere addedtoanother
10 1 L g l a s s v e s s e l e q u i p p e d w i t h a n a g i t a t o r a n d s u f f i c i e n t l y p u r g e d
with nitrogen. While the mixture was strongly stirred using a
homogenizer (model CLEARMIXCLM-1.5Sr manufacturedbyMTechnique
Co., Ltd.) at a rotation rate of 10,000 rpm and while liquid
temperature was maintained at OOc, 104 mmol of triethylaluminum
15 was slowly added dropwise. Thereafter, the liquid temperature
was raised to 80°c over 4 hours, and while temperature was
maintained at 80°c, 202 mmol of triethylaluminumwas again slowly
added dropwise. The mixture was reacted further for 1 hour.
After completion ofthe reaction, the solidportion was recovered
20 by filtration and washed sufficiently using dry toluene. Then
200 mL of dry toluene was added to produce a toluene slurry of
the solidcomponent (Y). Part ofthis toluene slurrywas sampled,
and particle diameter of the solid component (Y) measured by the
dynamic light scattering method was 750 nm.
[Preparation of Solid C a t a l y s t Component ( Z ) ]
100 mL of dry toluene was loaded i n t o a 300 mL g l a s s v e s s e l
equipped with an a g i t a t o r and s u f f i c i e n t l y purged with n i t r o g e n .
5.0 mmol (Mg atom b a s i s ) of the toluene s l u r r y of t h e s o l i d
5 component ( Y ) prepared as above were added. Thereafter, 7.0 mL
of a toluene s o l u t i o n of t r a n s i t i o n metal compound (B-2) (0.001
mmol/mL, Z r atom b a s i s ) was added dropwise, and t h e mixture was
reacted f o r 1 hour a t room temperature. After completion of the
r e a c t i o n , the supernatant l i q u i d was removed by decantation, and
10 the obtained s o l i d component was washed t h r e e t i m e s using dry
toluene and two t i m e s using dry decane t o prepare a decane s l u r r y
of the s o l i d c a t a l y s t component ( Z ) . A p a r t of t h e decane s l u r r y
of the s o l i d c a t a l y s t component ( Z ) obtained was c o l l e c t e d t o
examine the concentration. It was found t h a t Z r concentration
15 was 0.000234 mol/mL.
[Ethylene Polymerization]
500mLofdryheptanewasloadedintoa1Lautoclaveequipped
with an a g i t a t o r and s u f f i c i e n t l y purged with nitrogen. Then
ethylene was fed, and the l i q u i d phase and t h e gas phase were
20 s a t u r a t e d with e t h y l e n e . T h e r e a f t e r , 1.00 mmol (A1 atom b a s i s )
of triethylaluminum and 0.0001 m o l ( Z r atom b a s i s ) of t h e s o l i d
c a t a l y s t component ( Z ) were added. While ethylene was fed so as
t o m a i n t a i n t o t a l pressure at0.8MPa, t h e p o l y m e r i z a t i o n r e a c t i o n
was performed f o r 3 hours a t 7 0 ' ~ . After completion of the
polymerization, the obtained polymer was washed using hexane.
Then the polymer was s u b j e c t e d t o p r e l i m i n a r y d r y i n g a t 8 0 ' ~un der
vacuum for 1 hour. Then the polymer was vacuum dried f u r t h e r f o r
i 10 hours at l l O a C . 49.9 g of polyethylene w a s obtained.
5 C a t a l y t i c a c t i v i t y was 166.2 kg/mrnol-Zr-h, and [q] was 27.5 dL/g.
Whentheobtainedpolymerparticleswereobservedusinga scanning
electron microscope, agglomerates having f i n e - p a r t i c l e
morphology were not observed (FIG. 3 4 ) . Polymer fouling was not
observed (FIG. 35) when the condition of the polymerization
10 reactor was checked.
[0191]
The obtained polyethylene was used t o produce a press sheet
by the samemethodas describedinExample 1, andthe s t r e t c h r a t i o
and strength of the stretch-molded a r t i c l e were measured. The
15 r e s u l t s are shown i n Table 3. The obtained polyethylene had low
s t r e t c h a b i l i t y , and strength of the stretch-molded a r t i c l e was
low.
Table 1
Time
min
3 0
3 0
3 0
Pressure
MPa
atm.
pressure
0.8
0.3
Temperature
" C
10
5 0
5 0
Example 1
Example 2
Example 3
Complex
B-1
B- 1
B-2
Support
Type
A-1
A-2
A-3
Particle
diameter
(nm)
40
40
40
Table 1 (continued)
5 [0193]
Table 2
0.3
0.3
0.3
0.8
0.8
0.8
0.3
0.3
6 5
5 0
5 0
5 0
5 0
6 5
5 0
5 0
3 0
30
30
30
30
6 0
30
30
B-2
B-3
B- 3
B- 4
B-4
B-5
B-2
B-2
Example 4
Example 5
Example 6
Example 7
Example 8
Example 9
Example 10
Example 11
Example
12
Example
13
Example
14
A-3
A-4
A-5
A-6
A-5
A-7
A-8
, A-9
Step
(b)
temp.
"C
5 0
5 0
5 0
40
3 0
5 0
40
5 0
150
70
, 80
Step
(a
temp.
"C
5 0
5 0
5 0
Step
(a)
flow
rate
L/min
0.5
0.5
0.5
Complex
B-2
B-2
B-2
Support Step (b)
pressure
MPa
0.3
0.3
0.3
Type
A-10
A- 10
A- 10
Particle
diameter
(nm)
40
40
40
Step
(a)
time
min
15
15
7.5
Step
(b)
time
min
25
31
23
Table 2 (Continued)
[0194]
5 Table 3
Example
12
Example
13
Example
14
Table 3 (Continued)
Total
dL/g
33.9
34.7
34.1
Activity
kg/mmol-h
209.0
14 9.0
280.2
Comparative
Example 1
Comparative
Example 2
Comparative
Example 3
Comparative
Example 4
Asmade clear by comparison ofthe examples and comparative
Fine
particle
diameter
nm
305
257
286
Step
(a)
[rll
dL/g
18.2
20.8
18.2
Complex
B-1
B- 4
B- 1
B-2 '
Comparative
Example 1
Comparative
Example 2
Comparative
Example 3
Comparative
Example 4
examples, no fouling was observed by the ultrahigh molecular
Support
weight polyethylene polymerized in the examples of the present
Stretch
Ratio
fold
193
181
184
Type
-
-
W
Y
Activity
kg/mmol0h
24.9
19.5
31.6
166.2
Time
min
3 0
3 0
6 0
180
Temperature
"C
10
5 0
5 0
70
Particle
diameter
(nm)
-
-
5300
750
Strength
GPa
3.5
3.3
3.4
Pressure
MPa
atm.
pressure
0.3
0.8
0.8
[q]
dL/g
38
'
27
Fouling
O
O
0
Fine
particle
diameter
nm
not
observed
not
observed
not
observed
not
observed
Stretch
Ratio
fold
14 7
162
116
10 3
Strength
GPa
2.2
3.5
1.4
1.3
Fouling
-
X
X
0
0
116
invention, and thus t h e r e is the p o s s i b i l i t y of i n d u s t r i a l
production o f t h e ethylene-basedpolymerparticles, and there was
a tendency f o r strength of the obtained stretch-molded a r t i c l e
t o be high.
5
INDUSTRIAL APPLICABILITY
[0196]
Byuseofthemethodofproductionofethylene-basedpolymer
p a r t i c l e s according t o the present invention, fouling of the
10 polymerization reactor walls and a g i t a t o r blade by the
ethylene-basedpolymerparticles canbe suppressedtotheminimum
degree, and t h i s is economically advantageous i n i n d u s t r i a l
production due t o lack of plant shutdown or the l i k e . Moreover,
when the ethylene-basedpolymer p a r t i c l e s o b t a i n e d b y t h i s method
15 are stretch-molded, ahighstrengthmoldedarticlecanbeobtained.
Thus the ethylene-based polymer p a r t i c l e s can be used
advantageously f o r a b a t t e r y separator, gel spun f i b e r , sheet,
or the l i k e .
[0197]
Since strength is p a r t i c u l a r l y high f o r a stretch-molded
a r t i c l e formed using the solid-phase stretch-molding method, use
f o r solid-phase stretch-molding a p p l i c a t i o n s is advantageous.

117
CLAIMS
1. Amethodofproduction of ethylene-basedpolymerparticles;
wherein the method comprises the step of:
homopolymerizing ethylene or copolymerizing ethylene and
5 a linear or branched a-olefin having 3 to 20 carbon atoms in the
presence of an olefin polymerization catalyst comprising:
(A) fine particles having an average particle diameter
greater than or equal to 1 nm and less than or equal to 300 nm
obtained at least by the following two steps:
10 (Step 1) causing contact between a metal halide and an
alcohol in a hydrocarbon solvent;
(Step 2) causing contact between a component obtained by
(Step 1) and an organoaluminum compound and/or an
organoaluminumoxy compound; and
(B) a transition metal compound represented in following
General Formula (I) or (11) :
(In Formula (I), M is a transition metal atom of Group 4 or 5 in
the periodic table;
20 m is an integer ranging from 1 to 4;
R1 to R5 are the same or different and are a hydrogen atom,
halogen atom, hydrocarbon group, heterocyclic compound residue,
oxygen-containing group, nitrogen-containing group,
boron-containing 9rOuP1 sulfur-containing group,
phosphorous-containing group, silicon-containing group,
5 germanium-containing group, or tin-containing group, wherein a
ring is optionally formed by bonding together of at least 2 such
groups;
R~ is selected from the group consisting of a hydrogen atom,
hydrocarbon groups having 1 to 4 carbon atoms and composed of only
10 primary or secondary carbon atoms, aliphatic hydrocarbon groups
having at least 4 carbon atoms, aryl group-substituted alkyl
groups, monocyclic or bicyclic alicyclic hydrocarbon groups,
aromatic hydrocarbon groups, and halogen atoms;
n is a number satisfying valance number of M;
X is a hydrogen atom, halogen atom, hydrocarbon group,
oxygen-containing group I sulfur-containing group,
nitrogen-containing group I boron-containing group I
aluminum-containing group, phosphorous-containing group,
halogen-containing group, heterocyclic compound residue,
20 silicon-containing group, germanium-containing group, or
tin-containing group; wherein multiple groups indicated by X may
be the same or different when n is greater than or equal to 2;
andoptionallymultiple groups indicatedbyx forma ring bymutual
bonding)
(In Formula (11), M is titanium, zirconium, or hafnium;
I
I R" to R" may be the same or different and are a hydrogen
atom, halogen atom, hydrocarbon group, heterocyclic compound
5 residue, oxygen-containing group, nitrogen-containing group,
boron-containing I gr0uPt sulfur-containing group,
I
I
i phosphorous-containing group, silicon-containing group,
germanium-containing group, or tin-containing group, wherein two
or more adjacent groups may be optionally bonded together to form
10 a ring;
X' and x2 are the same or different and are a hydrocarbon
group, oxygen-containing group, sulfur-containing group,
silicon-containing group, hydrogen atom, or halogen atom; and
Y is a divalent hydrocarbon group, divalent halogenated
15 hydrocarbon group, divalent silicon-containing group, divalent
germanium-containing group, divalent tin-containing group, -0-,
-CO-, -S-, -SO-, -SO2-, -Ge-, -Sn-, -NR-, -P (R) -, -P (0) (R) -, -BR-,
or -AlR- [wherein R is the same or different and is a hydrogen
atom, halogen atom, hydrocarbon group, halogenated hydrocarbon
20 group, or alkoxy group]) ; and
( E ) a n i n t r i n s i c v i s c o s i t y [q] oftheethylene-basedpolymer
p a r t i c l e s , measured i n decalin a t 1 3 5 " ~ , is from 5 t o 50 dL/g.
2. The method of production of ethylene-based polymer
5 p a r t i c l e s according t o claim 1;
whereinthealcohol is acombinationoftwotypes of alcohols
selected fromalcohols h a v i n g l t o 25 carbonatoms; anddifference
I i n carbon number of the two types of alcohols is g r e a t e r than or
equal t o 4.
10
3. The method of production of ethylene-based polymer
p a r t i c l e s according t o claim 2;
wherein the two types of alcohols are a combination of an
alcohol having 2 t o 12 carbon atoms and an alcohol having 13 t o
15 25 carbon atoms.
4. The method of production of ethylene-based polymer
p a r t i c l e s according t o claim 2;
wherein the two types of alcohols are a combination of two
20 types of alcohols selected from alcohols having 2 t o 12 carbon
atoms.
5. The method of production of ethylene-based polymer
p a r t i c l e s according t o any one of claims 1 t o 4;
wherein M in General Formula (I) of the transition metal
compound (B) is a transition metal atom of Group 4 in the periodic
table;
m is 2;
R' is a group selected from linear or branched hydrocarbon
groups having 1 to 20 carbon atoms, alicyclic hydrocarbon groups
having3to20 carbonatoms, andaromatichydrocarbongroupshaving
6 to 20 carbon atoms;
R* to R5 may be the same or different and are a hydrogen atom,
10 halogen atom, or hydrocarbon group;
R6 is selected from aliphatic hydrocarbon groups having at
least 5 carbon atoms, aryl group-substituted alkyl groups,
monocyclicorbicyclicalicyclichydrocarbongroups, andaromatic
hydrocarbon groups; and
15 X is a hydrogen atom, halogen atom, or hydrocarbon group.
6. The method of production of ethylene-based polymer
particles according to any one of claims 1 to 5;
wherein the homopolymerization of ethylene, or the
20 copolymerization of ethylene with a linear or branched cx-olefin
having 3 to 20 carbon atoms, is performed in a multi-stage
polymerization.
Ethylene-basedpolymerparticles obtainedbytheproduction
b
122
method according to any one of claims 1 to 6;
I wherein an average particle diameter ofthe ethylene-based
I polymer particles is within a range greater than or equal to 10
nm and less than 3,000 nm.
5
8. A method of production of a stretch-molded article using
ethylene-based polymer particles obtained by the production
method according to any one of claims'l to 6.
10 9. Amethodofproductionofastretch-moldedarticleaccording
to claim 8 obtained by a solid-phase stretch-molding method.
10. A stretch-molded article obtained by the method according
to claim 8 or 9.